Substituted benzothiazols with herbicidal action

ABSTRACT

Substituted benzothiazoles I and their salts ##STR1## used as herbicides and for the desiccation/abscission of plants.

This application has been filed under 35 USC 371 as a national stageapplication of PCT/EP96/03760 filed Aug. 26, 1996.

The present invention relates to novel substituted benzothiazoles of thegeneral formula I ##STR2## where X¹ and X², independently of oneanother, are each oxygen or sulfur;

R¹ is hydrogen, amino, C₁ -C₆ -alkyl or C₁ -C₆ -haloalkyl;

R² is hydrogen, halogen, C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₁ -C₆-alkylthio, C₁ -C₆ -alkylsulfinyl or C₁ -C₆ -alkylsulfonyl;

R³ is hydrogen, halogen or C₁ -C₆ -alkyl;

R⁴ is hydrogen or halogen;

R⁵ is cyano, halogen, C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₁ -C₆ -alkoxyor C₁ -C₆ -haloalkoxy;

Y is a chemical bond, oxygen, sulfur, --SO-- or --SO₂ --;

R⁶ is hydrogen, cyano, halogen, C₃ -C₆ -cycloalkyl, C₁ -C₆ -haloalkyl,C₃ -C₆ -alkenyl, C₃ -C₆ -haloalkenyl, C₃ -C₆ -alkynyl or C₁ -C₆ -alkyl,it being possible for the stated cycloalkyl, alkyl, alkenyl and alkynylradicals to be substituted by cyano, C₁ -C₆ -alkoxy, C₁ -C₆ -alkylthio,(C₁ -C₆ -alkoxy)carbonyl, C₁ -C₆ -alkylaminocarbonyl, di(C₁ -C₆-alkyl)aminocarbonyl, (C₁ -C₆ -alkyl)carbonyloxy, halo-C₁ -C₆ -alkoxy,halo-C₁ -C₆ -alkylthio or C₃ -C₆ -cycloalkyl, with the proviso that R⁶may be cyano only when Y is a chemical bond, oxygen or sulfur and

R⁶ may be halogen only when Y is a chemical bond,

and the agriculturally useful salts of I.

The present invention furthermore relates to

the use of the compounds I as herbicides or for desiccating and/ordefoliating plants,

herbicides and plant desiccants/defoliants which contain the compounds Ias active ingredients,

processes for the preparation of the compounds I and of herbicides andplant desiccants/defoliants using the compounds I,

methods for controlling undesirable plant growth and for desiccatingand/or defoliating plants with the compounds I and

novel intermediates of the formulae IV, V, XI and XIV, from which thecompounds I are obtainable.

Herbicidal benzothiazoles having certain heterocycles in the 7 positionhave been disclosed in WO 92/20675 and DE-A 42 41 658. WO 92/20675 alsoindicates a possible desiccant/defoliant action of the compoundsdescribed there.

However, the herbicidal action of the known compounds with regard toweeds is not always completely satisfactory. It is an object of thepresent invention to provide novel benzothiazoles having improvedherbicidal properties. It is furthermore an object of the presentinvention to provide novel compounds having a desiccant/defoliantaction.

We have found that these objects are achieved by the substitutedbenzothiazoles of the formula I which are defined at the outset. We havealso found herbicides which contain the compounds I and have a very goodherbicidal action. We have furthermore found processes for thepreparation of these agents and methods for controlling undesirableplant growth with the compounds I.

Moreover, we have found that the compounds I are also suitable fordesiccating and defoliating plant parts in crops such as cotton, potato,rape, sunflower, soybean or field beans, in particular cotton. In thiscontext, we have found plant desiccants and/or defoliants, processes forthe preparation of these agents and methods for desiccating and/ordefoliating plants with the compounds I.

Depending on the substitution pattern, the compounds of the formula Imay contain one or more centers of chirality and may therefore bepresent as enantiomer or diastereomer mixtures. The present inventionrelates both to the pure enantiomers or diastereomers and to themixtures thereof.

The substituted benzothiazoles I may be present in the form of theiragriculturally useful salts, the type of salt being as a ruleunimportant. In general, suitable salts are the salts of those bases andthose acid addition salts in which the herbicidal action is notadversely affected in comparison with the free compound I.

Particularly suitable basic salts are those of the alkali metals,preferably the sodium and potassium salts, those of the alkaline earthmetals, preferably calcium and magnesium salts, those of the transitionmetals, preferably zinc and iron salts, and ammonium salts in which theammonium ion may, if desired, carry from one to four C₁ -C₄ -alkyl orhydroxy-C₁ -C₄ -alkyl substituents and/or a phenyl or benzylsubstituent, preferably diisopropylammonium, tetramethylammonium,tetrabutylammonium, trimethylbenzylammonium andtrimethyl-(2-hydroxyethyl)ammonium salts, and phosphonium salts,sulfonium salts, preferably tri(C₁ -C₄ -alkyl)sulfonium salts, andsulfoxonium salts, preferably tri(C₁ -C₄ -alkyl)sulfoxonium salts.

Examples of the acid addition salts are primarily the hydrochlorides andhydrobromides, sulfates, nitrates, phosphates, oxalates anddodecylbenzenesulfonates.

The organic moieties stated in the definition of the substituents R¹ toR⁶ are--as in the case of halogen--general terms for individual lists ofthe individual group members. All carbon chains, ie. all alkyl,haloalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkoxy,haloalkylthio, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,alkylcarbonyloxy, alkenyl, haloalkenyl and alkynyl moieties, may bestraight-chain or branched. Polyhalogenated haloalkyl, haloalkoxy,haloalkylthio and haloalkenyl radicals may carry identical or differenthalogen atoms.

The specific meanings are, for example, as follows:

halogen: fluorine, chlorine, bromine or iodine;

C₁ -C₆ -alkyl and the alkyl moieties of (C₁ -C₆ -alkyl)carbonyloxy, C₁-C₆ -alkylaminocarbonyl, di(C₁ -C₆ -alkyl)aminocarbonyl, (C₁ -C₆-alkyl)carbonyloxy-C₁ -C₆ -alkyl, C₁ -C₆ -alkylaminocarbonyl-C₁ -C₆-alkyl, di(C₁ -C₆ -alkyl)aminocarbonyl-C₁ -C₆ -alkyl, C₁ -C₆-alkylaminocarbonyl-C₃ -C₆ -alkenyl, di(C₁ -C₆ -alkyl)aminocarbonyl-C₃-C₆ -alkenyl, C₁ -C₆ -allylaminocarbonyl-C₃ -C₆ -alkynyl, di(C₁ -C₆-alkyl)aminocarbonyl-C₃ -C₆ -alkynyl, C₁ -C₆ -alkylaminocarbonyl-C₃ -C₆-cycloalkyl and di(C₁ -C₆ -alkyl)aminocarbonyl-C₃ -C₆ -cycloalkyl:methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl,2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl,n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and1-ethyl-2-methylpropyl;

cyano-C₁ -C₆ -alkyl: for example cyanomethyl, 1-cyanoethyl,2-cyanoethyl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-1-yl,1-cyanobut-1-yl, 2-cyanobut-1-yl, 3-cyanobut-1-yl, 4-cyanobut-1-yl,1-cyanobut-2-yl, 2-cyanobut-2-yl, 3-cyanobut-2-yl, 4-cyanobut-2-yl,1-(cyanomethyl)-eth-1-yl, 1-(cyanomethyl)-1-(methyl)-eth-1-yl,1-(cyanomethyl)prop-1-yl and 2-cyanohex-6-yl;

C₁ -C₆ -haloalkyl: C₁ -C₆ -alkyl as stated above, which is partially orcompletely substituted by fluorine, chlorine, bromine and/or iodine, eg.chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl,difluoromethyl, trifluoromethyl, chlorofluoromethyl,dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl,2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl,2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,2,2,2-trichloroethyl, petafluoroethyl sic!, 2-fluoropropyl,3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl,3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl,3,3,3-trifluoropropyl, 3,3,3-trichloropropyl,2,2,3,3,3-pentafluoropropyl, heptaluoropropyl,1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl,1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyland nonafluorobutyl, 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl,5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl,6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;

C₁ -C₆ -alkoxy and the alkoxy moieties of C₁ -C₆ -alkoxy-C₁ -C₆ -alkyl,C₁ -C₆ -alkoxy-C₃ -C₆ -alkenyl, C₁ -C₆ -alkoxy-C₃ -C₆ -alkynyl, C₁ -C₆-alkoxy-C₃ -C₆ -cycloalkyl, (C₁ -C₆ -alkoxy)carbonyl, (C₁ -C₆-alkoxy)carbonyl-C₁ -C₆ -alkyl, (C₁ -C₆ -alkoxy)carbonyl-C₃ -C₆-alkenyl, (C₁ -C₆ -alkoxy)carbonyl-C₃ -C₆ -alkynyl sic! and (C₁ -C₆-alkoxy)carbonyl-C₃ -C₆ -cycloalkyl: methoxy, ethoxy, n-propoxy,1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy,1,1-dimethylethoxy, n-pentyloxy, 1-methylbutoxy, 2-methylbutoxy,3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy,2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexyloxy, 1-methylpentyloxy,2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy,1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy,2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy,1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy,1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and1-ethyl-2-methylpropoxy;

C₁ -C₆ -haloalkoxy and the haloalkoxy moieties of C₁ -C₆ -haloalkoxy-C₁-C₆ -alkyl, C₁ -C₆ -haloalkoxy-C₃ -C₆ -alkenyl, C₁ -C₆ -haloalkoxy-C₃-C₆ -alkynyl and C₁ -C₆ -haloalkoxy-C₃ -C6-Cycloalkyl: C₁ -C₆ -alkoxy asstated above, which is partially or completely substituted by fluorine,chlorine, bromine and/or iodine, eg. chloromethoxy, dichloromethoxy,trichloromethyloxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy,chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy,2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy,2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,2,2,2-trichloroethoxy, petafluoroethoxy sic!, 2-fluoropropoxy,3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy,2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy,3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy,2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy,1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy,1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy,4-bromobutoxy and nonafluorobutoxy, 5-fluoropentyloxy,5-chloropentyloxy, 5-bromopentyloxy, 5-iodopentyloxy,undecafluoropentyloxy, 6-fluorohexyloxy, 6-chlorohexyloxy,6-bromohexyloxy, 6-iodohexyloxy and dodecafluorohexyloxy;

C₁ -C₆ -alkylthio and the alkylthio moieties Of C₁ -C₆ -alkylthio-C₁ -C₆-alkyl, C₁ -C₆ -alkylthio-C₃ -C₆ -alkenyl, C₁ -C₆ -alkylthio-C₃ -C₆-alkynyl and C₁ -C₆ -alkylthio-C₃ -C₆ -cycloalkyl: methylthio,ethylthio, n-propylthio, 1-methylethylthio, n-butylthio,1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio,n-pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio,2,2-dimethylpropylthio, 1-ethylpropylthio, n-hexylthio,1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio,2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1, 3-dimethylbutylthio,2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio,1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio,1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and1-ethyl-2-methylpropylthio, preferably methylthio and ethylthio;

C₁ -C₆ -haloalkylthio and the haloalkylthio moieties of C₁ -C₆-haloalkylthio-C₁ -C₆ -alkyl, C₁ -C₆ -haloalkylthio-C₃ -C₆ -alkenyl, C₁-C₆ -haloalkylthio-C₃ -C₆ -alkynyl and C₁ -C₆ -haloalkylthio-C₃ -C₆-cycloalkyl: C₁ -C₆ -alkylthio as stated above, which is partially orcompletely substituted by fluorine, chlorine and/or bromine, eg.difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio,bromodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio,2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2, 2-trichloroethylthio,2-chloro-2-fluoroethylthio, 2-chloro-2, 2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, pentafluoroethylthio, 2-fluoropropylthio,3-fluoropropylthio, 2-chloropropylthio, 3-chloropropylthio,2-bromopropylthio, 3-bromopropylthio, 2,2-difluoropropylthio,2,3-difluoropropylthio, 2,3-dichloropropylthio, 3,3,3-trifluoropropylthio, 3,3, 3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio, 1-(chloromethyl )-2-chloroethylthio, 1-(bromomethyl)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio,4-bromobutylthio, 5-fluoropentylthio, 5-chloropentylthio,5-bromopentylthio, 5-iodopentylthio, andecafluoropentylthio,6-fluorohexylthio and 6-chlorohexylthio;

C₁ -C₆ -alkylsulfinyl, such as methylsulfinyl, ethylsulfinyl,n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl,1-methylpropylsulfinyl, 2-methylpropylsulfinyl,1,1-dimethylethylsulfinyl, n-pentylsulfinyl, 1-methylbutylsulfinyl,2-methylbutylsulfinyl, 3-methylbutylsulfinyl,1,1-dimethylipropylsulfinyl, 1,2-dimethylpropylsulfinyl,2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, n-hexylsulfinyl,1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl,4-methylpentylsulfinyl, 1,1-dimethylbutylsulfinyl,1,2-dimethylbutylsulfinyl, 1,3-dimethylbutylsulfinyl,2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl,3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl,1,1,2-trimethylpropylsulfinyl, 1,2,2-trimethylpropylsulfinyl,1-ethyl-1-methylpropylsulfinyl and 1-ethyl-2-methylpropylsulfinyl;

C₁ -C₆ -alkylsulfonyl: methylsulfonyl, ethylsulfonyl, n-propylsulfonyl,1-methylethylsulfonyl, n-butylsulfonyl, 1-methylpropylsulfonyl,2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, n-pentylsulfonyl,1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl,1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl,2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, n-hexylsulfonyl,1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl,4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl,1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl,2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl,3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl,1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl,1-ethyl-l-methylpropylsulfonyl and 1-ethyl-2-methylpropylsulfonyl;

C₃ -C₆ -cycloalkyl and the cycloalkyl moieties of C₃ -C₆ -cycloalkyl-C₃-C₆ -alkenyl, C₁ -C₆ -cycloalkyl-C₃ -C₆ -alkynyl and C₃ -C₆-Cycloalkyl-C₃ -C₆ -cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl andcyclohexyl;

C₃ -C₆ -cycloalkyl-C₁ -C₆ -alkyl: for example cyclopropylmethyl,cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl,2-(cyclopropyl)ethyl, 2-(cyclobutyl)ethyl, 2-(cyclopentyl)ethyl,2-(cyclohexyl)ethyl, 3-(cyclopropyl)propyl, 3-(cyclobutyl)propyl,3-(cyclopentyl)propyl, 3-(cyclohexyl)propyl, 4-(cyclopropyl)butyl,4-(cyclobutyl)butyl, 4-(cyclopentyl)butyl, 4-(cyclohexyl)butyl,5-(cyclopropyl)pentyl, 5-(cyclobutyl)pentyl, 5-(cyclopentyl)pentyl,5-(cyclohexyl)pentyl, 6-(cyclopropyl)hexyl, 6-(cyclobutyl)hexyl,6-(cyclopentyl)hexyl and 6-(cyclohexyl)hexyl;

C₃ -C₆ -alkenyl and the alkenyl moieties of C₁ -C₆ -alkoxy-C₃ -C₆-alkenyl, C₁ -C₆ -alkylthio-C₃ -C₆ -alkenyl, (C₁ -C₆ -alkoxy)carbonyl-C₃-C₆ -alkenyl, C₁ -C₆ -alkylaminocarbonyl-C₃ -C₆ -alkenyl, di(C₁ -C₆-alkyl)aminocarbonyl-C₃ -C₆ -alkenyl, (C₁ -C₆ -alkyl)carbonyloxy-C₃ -C₆-alkenyl, C₁ -C₆ -haloalkoxy-C₃ -C₆ -alkenyl, C₁ -C₆ -haloalkylthio-C₃-C₆ -alkenyl and C₃ -C₆ -cycloalkyl-C₃ -C₆ -alkenyl: prop-1-en-1-yl,prop-2-en-1-yl, 1-methyl-ethenyl, n-buten-1-yl, n-buten-2-yl,n-buten-3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl,1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, n-penten-1-yl,n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methyl-but-1-en-1-yl,2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl,2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl,2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl,1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl,1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl,1-ethylprop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl,n-hex-3-en-1-yl, n-hex-4-en-1-yl, n-hex-5-en-1-yl,1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl,4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl,3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl,2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl,1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl,4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl,1,1-dimethyl-but-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl,1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl,1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl,1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl,2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl,2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl,3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl,1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl,2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl,1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl and1-ethyl-2-methylprop-2-en-1-yl;

cyano-C₃ -C₆ -alkenyl: for example 2-cyanoallyl, 3-cyanoallyl,4-cyanobut-2-enyl, 4-cyanobut-3-enyl and 5-cyanopent-4-enyl;

C₃ -C₆ -haloalkenyl: C₃ -C₆ -alkenyl as stated above, which is partiallyor completely substituted by fluorine, chlorine, bromine and/or iodine,eg. 2-chloroallyl, 3-chloroallyl, 2,3-dichloroallyl, 3,3-dichloroallyl,2,3,3-trichloroallyl, 2,3-dichlorobut-2-enyl, 2-bromoallyl,3-bromoallyl, 2,3-dibromoallyl, 3,3-dibromoallyl, 2,3,3-tribromoallyland 2,3-dibromobut-2-enyl;

C₃ -C₆ -alkynyl and the alkynyl moieties of C₁ -C₆ -alkoxy-C₃ -C₆-alkynyl, C₁ -C₆ -alkylthio-C₃ -c6-alkynyl, (C₁ -C₆ -alkoxy)carbonyl-C₃-C₆ -alkynyl, C₁ -C₆ -alkylaminocarbonyl-C₃ -C₆ -alkynyl, di(C₁ -C₆-alkyl)aminocarbonyl-C₃ -C₆ -alkynyl, (C₁ -C₆ -alkyl)carbonyloxy-C₃ -C₆-alkynyl, C₁ -C₆ -haloalkoxy-C₃ -C₆ -alkynyl, C₁ -C₆ -haloalkylthio-C₃-C₆ -alkynyl and C₃ -C₆ -cycloalkyl-C₃ -C₆ -alkynyl: prop-1-yn-1-yl,prop-2-yn-1-yl, n-but-1-yn-1-yl, n-but-1-yn-3-yl, n-but-1-yn-4-yl,n-but-2-yn-1-yl, n-pent-1-yn-1-yl, n-pent-1-yn-3-yl, n-pent-1-yn-4-yl,n-pent-1-yn-5-yl, n-pent-2-yn-1-yl, n-pent-2-yn-4-yl, n-pent-2-yn-5-yl,3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, n-hex-1-yn-1-yl,n-hex-1-yn-3-yl, n-hex-1-yn-4-yl, n-hex-1-yn-5-yl, n-hex-1-yn-6-yl,n-hex-2-yn-1-yl, n-hex-2-yn-4-yl, n-hex -2-yn-5-yl , n-hex -2-yn -6-yl ,n-hex -3-yn -1-yl, n-hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl,3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl,4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl and4-methylpent-2-yn-5-yl;

cyano-C₃ -C₆ -alkynyl: for example 3-cyanopropargyl,4-cyanobut-2-yn-1-yl, 5-cyanopent-3-yn-1-yl and 6-cyanohex-4-yn-1-yl.

In view of the use of the novel compounds of the formula I as herbicidesor as compounds having a desiccant/defoliant action, the variablespreferably have the following meanings, alone or in combination:

X¹ is oxygen;

X² is oxygen or sulfur, in particular oxygen;

R¹ is amino, C₁ -C₆ -alkyl or C₁ -C₆ -haloalkyl, in particular amino orC₁ -C₆ -alkyl, particularly preferably methyl;

R² is halogen, C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl or C₁ -C₆-alkylsulfonyl, in particular C₁ -C₆ -haloalkyl, particularly preferablytrifluoromethyl, chlorodifluoromethyl or pentafluoroethyl, veryparticularly preferably trifluoromethyl;

R³ is hydrogen or halogen, in particular hydrogen;

R⁴ is hydrogen, fluorine or chlorine;

R⁵ is cyano or halogen, in particular cyano, chlorine or bromine,particularly preferably chlorine;

Y is a chemical bond, sulfur, --SO-- or --SO₂ --, in particular achemical bond or sulfur;

R⁶ is hydrogen, halogen, C₃ -C₆ -cycloalkyl, C₁ -C₆ -haloalkyl, C₃ -C₆-alkenyl or C₁ -C₆ -alkyl, it being possible for the stated cycloalkyl,alkyl and alkenyl radicals to be substituted by cyano, C₁ -C₆ -alkoxy,(C₁ -C₆ -alkoxy)carbonyl, (C₁ -C₆ -alkyl)carbonyloxy or C₁ -C₆-haloalkoxy, with the proviso that R⁶ may be halogen only when Y is achemical bond.

Particularly preferred compounds of the formula I are those in which R⁶is one of the radicals 6.5-6.63 or, when Y is a chemical bond, also oneof the radicals 6.1-6.04 (Table 1):

                  TABLE 1    ______________________________________    No.            R.sup.6    ______________________________________    6.1            F    6.2            Cl    6.3            Br    6.4            I    6.5            H    6.6            CH.sub.2 Cl    6.7            CH.sub.2 F    6.8            CHF.sub.2    6.9            CF.sub.3    6.10           CClF.sub.2    6.11           CCl.sub.2 F    6.12           CH.sub.2 CH.sub.2 CN    6.13           CH.sub.2 CH.sub.2 F    6.14           CH.sub.2 CH.sub.2 Cl    6.15           CH.sub.2 CH.sub.2 Br    6.16           CH.sub.2 CH.sub.2 I    6.17           CH.sub.2 CF.sub.3    6.18           CF.sub.2 CF.sub.3    6.19           CH.sub.2 CH═CH.sub.2    6.20           CH(CH.sub.3)CH═CH.sub.2    6.21           CH.sub.2 CH═CH--CH.sub.3    6.22           CH(CH.sub.3)CH═CH--CH.sub.3    6.23           CH.sub.2 --C.tbd.CH    6.24           CH(CH.sub.3)C.tbd.CH    6.25           CH.sub.3    6.26           CH.sub.2 CH.sub.3    6.27           n-C.sub.3 H.sub.7    6.28           i-C.sub.3 H.sub.7    6.29           n-C.sub.4 H.sub.9    6.30           i-C.sub.4 H.sub.9    6.31           s-C.sub.4 H.sub.9    6.32           t-C.sub.4 H.sub.9    6.33           n-C.sub.5 H.sub.11    6.34           n-C.sub.6 H.sub.13    6.35           CH.sub.2 CN    6.36           CH(CH.sub.3)CN    6.37           CH.sub.2 CH(CH.sub.3)CN    6.38           CH(CH.sub.3)CH.sub.2 CN    6.39           CH.sub.2 CH.sub.2 OCH.sub.3    6.40           CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3    6.41           CH(CH.sub.3)CH.sub.2 OCH.sub.3    6.42           CH(CH.sub.3)CH.sub.2 OCH.sub.2 CH.sub.3    6.43           CH.sub.2 COOCH.sub.3    6.44           CH.sub.2 COOCH.sub.2 CH.sub.3    6.45           CH.sub.2 COOCH(CH.sub.3).sub.2    6.46           CH(CH.sub.3)COOCH.sub.3    6.47           CH(CH.sub.3)COOCH.sub.2 CH.sub.3    6.48           CH(CH.sub.3)COOCH(CH.sub.3).sub.2    6.49           CH.sub.2 CH.sub.2 COOCH.sub.3    6.50           CH.sub.2 CH.sub.2 COOCH.sub.2 CH.sub.3    6.51           CH(CH.sub.2 CH.sub.3)COOCH.sub.3    6.52           CH(CH.sub.2 CH.sub.3)COOCH.sub.2 CH.sub.3    6.53           CH(CH(CH.sub.3).sub.2)COOCH.sub.3    6.54           CH(CH(CH.sub.3).sub.2)COOCH.sub.2 CH.sub.3    6.55           CH.sub.2 CH.sub.2 OCOCH.sub.3    6.56           CH.sub.2 CH.sub.2 OCOCH.sub.2 CH.sub.3    6.57           CH(CH.sub.3)CH.sub.2 OCOCH.sub.3    6.58           CH.sub.2 CH(CH.sub.3)OCOCH.sub.3    6.59           CH.sub.2 CH.sub.2 OCHF.sub.2    6.60           CH.sub.2 CH.sub.2 OCH.sub.2 CF.sub.3    6.61           cyclohexyl    6.62           CH═CH--COOCH.sub.3    6.63           CH═CH--COOCH.sub.2 CH.sub.3    ______________________________________

With regard to the use of the substituted benzothiazoles of the formulaI as herbicides, the benzothiazoles Ia (═I where R¹ ═CH₃, R² ═CF₃, R³═H, R⁵ ═Cl, X¹ and X² ═O and Y═a chemical bond), in particular thecompounds Ia.1 to Ia.186 of Table 2, are very particularly preferred:

                  TABLE 2    ______________________________________     ##STR3##    No.         R.sup.4   R.sup.6    ______________________________________    Ia.1        H         Cl    Ia.2        F         Cl    Ia.3        Cl        Cl    Ia.4        H         Br    Ia.5        F         Br    Ia.6        Cl        Br    Ia.7        H         I    Ia.8        F         I    Ia.9        Cl        I    Ia.10       H         F    Ia.11       F         F    Ia.12       Cl        F    Ia.13       H         H    Ia.14       F         H    Ia.15       Cl        H    Ia.16       H         CH.sub.3    Ia.17       F         CH.sub.3    Ia.18       Cl        CH.sub.3    Ia.19       H         CH.sub.2 CH.sub.3    Ia.20       F         CH.sub.2 CH.sub.3    Ia.21       Cl        CH.sub.2 CH.sub.3    Ia.22       H         CH.sub.2 CH.sub.2 CH.sub.3    Ia.23       H         CH.sub.2 CH.sub.2 CH.sub.3    Ia.24       Cl        CH.sub.2 CH.sub.2 CH.sub.3    Ia.25       H         CH(CH.sub.3).sub.2    Ia.26       F         CH(CH.sub.3).sub.2    Ia.27       Cl        CH(CH.sub.3).sub.2    Ia.28       H         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3    Ia.29       F         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3    Ia.30       Cl        CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3    Ia.31       H         CHCH(CH.sub.3).sub.2    Ia.32       F         CHCH(CH.sub.3).sub.2    Ia.33       Cl        CHCH(CH.sub.3).sub.2    Ia.34       H         C(CH.sub.3).sub.3    Ia.35       F         C(CH.sub.3).sub.3    Ia.36       H         C(CH.sub.3).sub.3    Ia.37       H         CH(CH.sub.3)CH.sub.2 CH.sub.3    Ia.38       F         CH(CH.sub.3)CH.sub.2 CH.sub.3    Ia.39       Cl        CH(CH.sub.3)CH.sub.2 CH.sub.3    Ia.40       H         CH.sub.2 CHCH.sub.2    Ia.41       F         CH.sub.2 CHCH.sub.2    Ia.42       Cl        CH.sub.2 CHCH.sub.2    Ia.43       H         CH(CH.sub.3)CHCH.sub.2    Ia.44       F         CH(CH.sub.3)CHCH.sub.2    Ia.45       Cl        CH(CH.sub.3)CHCH.sub.2    Ia.46       H         CH.sub.2CHCH.sub.2CH.sub.3    Ia.47       F         CH.sub.2CHCH.sub.2CH.sub.3    Ia.48       Cl        CH.sub.2CHCH.sub.2CH.sub.3    Ia.49       H         CH(CH.sub.3)CHCHCH.sub.3    Ia.50       F         CH(CH.sub.3)CHCHCH.sub.3    Ia.51       Cl        CH(CH.sub.3)CHCHCH.sub.3    Ia.52       H         CH.sub.2 C CH    Ia.53       F         CH.sub.2 C CH    Ia.54       Cl        CH.sub.2 C CH    Ia.55       H         CH(CH.sub.3)C CH    Ia.56       F         CH(CH.sub.3)C CH    Ia.57       Cl        CH(CH.sub.3)C CH    Ia.58       H         CH.sub.2 C CCH.sub.3    Ia.59       F         CH.sub.2 C CCH.sub.3    Ia.60       Cl        CH.sub.2 C CCH.sub.3    Ia.61       H         CH.sub.2 Cl    Ia.62       F         CH.sub.2 Cl    Ia.63       Cl        CH.sub.2 Cl    Ia.64       H         CH.sub.2 F    Ia.65       F         CH.sub.2 F    Ia.66       Cl        CH.sub.2 F    Ia.67       H         CHF.sub.2    Ia.68       F         CHF.sub.2    Ia.69       Cl        CHF.sub.2    Ia.70       H         CF.sub.3    Ia.71       F         CF.sub.3    Ia.72       Cl        CF.sub.3    Ia.73       H         CClF.sub.2    Ia.74       F         CClF.sub.2    Ia.75       Cl        CClF.sub.2    Ia.76       H         CCl.sub.2 F    Ia.77       F         CCl.sub.2 F    Ia.78       Cl        CCl.sub.2 F    Ia.79       H         CH.sub.2 CHF.sub.2    Ia.80       F         CH.sub.2 CHF.sub.2    Ia.81       Cl        CH.sub.2 CHF.sub.2    Ia.82       H         CH.sub.2 CH.sub.2 F    Ia.83       F         CH.sub.2 CH.sub.2 F    Ia.84       Cl        CH.sub.2 CH.sub.2 F    Ia.85       H         CH.sub.2 CH.sub.2 Cl    Ia.86       F         CH.sub.2 CH.sub.2 Cl    Ia.87       Cl        CH.sub.2 CH.sub.2 Cl    Ia.88       H         CH.sub.2 CH.sub.2 Br    Ia.89       F         CH.sub.2 CH.sub.2 Br    Ia.90       Cl        CH.sub.2 CH.sub.2 Br    Ia.91       H         CH.sub.2 CH.sub.2 I    Ia.92       F         CH.sub.2 CH.sub.2 I    Ia.93       Cl        CH.sub.2 CH.sub.2 I    Ia.94       H         CH.sub.2 CF.sub.3    Ia.95       F         CH.sub.2 CF.sub.3    Ia.96       Cl        CH.sub.2 CF.sub.3    Ia.97       H         CF.sub.2 CF.sub.3    Ia.98       F         CF.sub.2 CF.sub.3    Ia.99       Cl        CF.sub.2 CF.sub.3    Ia.100      H         CH.sub.2 CN    Ia.101      F         CH.sub.2 CN    Ia.102      Cl        CH.sub.2 CN    Ia.103      H         CH(CH.sub.3)CN    Ia.104      F         CH(CH.sub.3)CN    Ia.105      Cl        CH(CH.sub.3)CN    Ia.106      H         CH.sub.2 CH.sub.2 CN    Ia.107      F         CH.sub.2 CH.sub.2 CN    Ia.108      Cl        CH.sub.2 CH.sub.2 CN    Ia.109      H         CH(CH.sub.3)CH.sub.2 CN    Ia.110      F         CH(CH.sub.3)CH.sub.2 CN    Ia.111      Cl        CH(CH.sub.3)CH.sub.2 CN    Ia.112      H         CH.sub.2 CH.sub.2 OCH.sub.3    Ia.113      F         CH.sub.2 CH.sub.2 OCH.sub.3    Ia.114      Cl        CH.sub.2 CH.sub.2 OCH.sub.3    Ia.115      H         CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3    Ia.116      F         CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3    Ia.117      Cl        CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3    Ia.118      H         CH(CH.sub.3)CH.sub.2 OCH.sub.3    Ia.119      F         CH(CH.sub.3)CH.sub.2 OCH.sub.3    Ia.120      Cl        CH(CH.sub.3)CH.sub.2 OCH.sub.3    Ia.121      H         CH(CH.sub.3)CH.sub.2 OCH.sub.2 CH.sub.3    Ia.122      F         CH(CH.sub.3)CH.sub.2 OCH.sub.2 CH.sub.3    Ia.123      Cl        CH(CH.sub.3)CH.sub.2 OCH.sub.2 CH.sub.3    Ia.124      H         CH.sub.2 COOCH.sub.3    Ia.125      F         CH.sub.2 COOCH.sub.3    Ia.126      Cl        CH.sub.2 COOCH.sub.3    Ia.127      H         CH.sub.2 COOCH.sub.2 CH.sub.3    Ia.128      F         CH.sub.2 COOCH.sub.2 CH.sub.3    Ia.129      Cl        CH.sub.2 COOCH.sub.2 CH.sub.3    Ia.130      H         CH.sub.2 COOCH(CH.sub.3).sub.2    Ia.131      F         CH.sub.2 COOCH(CH.sub.3).sub.2    Ia.132      Cl        CH.sub.2 COOCH(CH.sub.3).sub.2    Ia.133      H         CH(CH.sub.3)COOCH.sub.3    Ia.134      F         CH(CH.sub.3)COOCH.sub.3    Ia.135      Cl        CH(CH.sub.3)COOCH.sub.3    Ia.136      H         CH(CH.sub.3)COOCH.sub.2 CH.sub.3    Ia.137      F         CH(CH.sub.3)COOCH.sub.2 CH.sub.3    Ia.138      Cl        CH(CH.sub.3)COOCH.sub.2 CH.sub.3    Ia.139      H         CH(CH.sub.3)COOCH(CH.sub.3).sub.2    Ia.140      F         CH(CH.sub.3)COOCH(CH.sub.3).sub.2    Ia.141      Cl        CH(CH.sub.3)COOCH(CH.sub.3).sub.2    Ia.142      H         CH.sub.2 CH.sub.2 COOCH.sub.3    Ia.143      F         CH.sub.2 CH.sub.2 COOCH.sub.3    Ia.144      Cl        CH.sub.2 CH.sub.2 COOCH.sub.3    Ia.145      H         CH.sub.2 CH.sub.2 COOCH.sub.2 CH.sub.3    Ia.146      F         CH.sub.2 CH.sub.2 COOCH.sub.2 CH.sub.3    Ia.147      Cl        CH.sub.2 CH.sub.2 COOCH.sub.2 CH.sub.3    Ia.148      H         CH(CH.sub.2 CH.sub.3)COOCH.sub.3    Ia.149      F         CH(CH.sub.2 CH.sub.3)COOCH.sub.3    Ia.150      Cl        CH(CH.sub.2 CH.sub.3)COOCH.sub.3    Ia.151      H         CH(CH.sub.2 CH.sub.3)COOCH.sub.2 CH.sub.3    Ia.152      F         CH(CH.sub.2 CH.sub.3)COOCH.sub.2 CH.sub.3    Ia.153      Cl        CH(CH.sub.2 CH.sub.3)COOCH.sub.2 CH.sub.3    Ia.154      H         CH CH(CH.sub.3).sub.2 !COOCH.sub.3    Ia.155      F         CH CH(CH.sub.3).sub.2 !COOCH.sub.3    Ia.156      Cl        CH CH(CH.sub.3).sub.2 !COOCH.sub.3    Ia.157      H         CH.sub.2 CH.sub.2 OCOCH.sub.3    Ia.158      F         CH.sub.2 CH.sub.2 OCOCH.sub.3    Ia.159      Cl        CH.sub.2 CH.sub.2 OCOCH.sub.3    Ia.160      H         CH.sub.2 CH.sub.2 OCOCH.sub.2 CH.sub.3    Ia.161      F         CH.sub.2 CH.sub.2 OCOCH.sub.2 CH.sub.3    Ia.162      Cl        CH.sub.2 CH.sub.2 OCOCH.sub.2 CH.sub.3    Ia.163      H         CH(CH.sub.3)CH.sub.2 OCOCH.sub.3    Ia.164      F         CH(CH.sub.3)CH.sub.2 OCOCH.sub.3    Ia.165      Cl        CH(CH.sub.3)CH.sub.2 OCOCH.sub.3    Ia.166      H         CH.sub.2 CH(CH.sub.3)OCOCH.sub.3    Ia.167      F         CH.sub.2 CH(CH.sub.3)OCOCH.sub.3    Ia.168      Cl        CH.sub.2 CH(CH.sub.3)OCOCH.sub.3    Ia.169      H         CH.sub.2 CH.sub.2 OCHF.sub.2    Ia.170      F         CH.sub.2 CH.sub.2 OCHF.sub.2    Ia.171      Cl        CH.sub.2 CH.sub.2 OCHF.sub.2    Ia.172      H         CH.sub.2 CH.sub.2 OCH.sub.2 CF.sub.3    Ia.173      F         CH.sub.2 CH.sub.2 OCH.sub.2 CF.sub.3    Ia.174      Cl        CH.sub.2 CH.sub.2 OCH.sub.2 CF.sub.3    Ia.175      H         cyclohexyl    Ia.176      F         cyclohexyl    Ia.177      Cl        cyclohexyl    Ia.178      H         CHCHCOOCH.sub.3    Ia.179      F         CHCHCOOCH.sub.3    Ia.180      Cl        CHCHCOOCH.sub.3    Ia.181      H         CHCHCOOCH.sub.2 CH.sub.3    Ia.182      F         CHCHCOOCH.sub.2 CH.sub.3    Ia.183      Cl        CHCHCOOCH.sub.2 CH.sub.3    Ia.184      H         CN    Ia.185      F         CN    Ia.186      Cl        CN    ______________________________________

furthermore, the following substituted benzothiazoles of the formulae Ibto Iu are vary particularly preferred, in particular:

the compounds Ib.1 to Ib.186, which differ from the compounds Ia.1 toIa.186 only in that R¹ is amino: ##STR4## the compounds Ic.13 to Ic.186,which differ from the compounds Ia.13 to Ia.186 only in that Y isoxygen: ##STR5## the compounds Id.13 to Id.186, which differ from thecompounds Ia.13 to Ia.186 only in that R¹ is amino and Y is oxygen:##STR6## the compounds Ie.13 to Ie.186, which differ from the compoundsIa.13 to Ia.186 only in that Y is sulfur: ##STR7## the compounds If.13to If.186, which differ from the compounds Ia.13 to Ia.186 only in thatR¹ is amino and Y is sulfur: ##STR8## the compounds Ig.13 to Ig.183,which differ from the compounds Ia.13 to Ia.183 only in that Y is--SO--: ##STR9## the compounds Ih.13 to Ih.183, which differ from thecompounds Ia.13 to Ia.183 only in that R¹ is amino and Y is --SO--:##STR10## the compounds Ii.13 to Ii.183, which differ from the compoundsIa.13 to Ia.183 only in that Y is --SO₂ --: ##STR11## the compoundsIk.13 to Ik.183, which differ from the compounds Ia.13 to Ia.183 only inthat R¹ is amino and Y is --SO₂ --: ##STR12## the compounds Il.1 toIl.186, which differ from the compounds Ia.1 to Ia.186 only in that R⁵is cyano: ##STR13## the compounds Im.1 to Im.186, which differ from thecompounds Ia.1 to Ia.186 only in that R¹ is amino and R⁵ is cyano:##STR14## the compounds In.13 to In.186, which differ from the compoundsIa.13 to Ia.186 only in that Y is oxygen and R⁵ is cyano: ##STR15## thecompounds Io.13 to Io.186, which differ from the compounds Ia.13 toIa.186 only in that R¹ is amino, R⁵ is cyano and Y is oxygen: ##STR16##the compounds Ip.13 to Ip.186, which differ from the compounds Ia.13 toIa.186 only in that Y is sulfur and R⁵ is cyano: ##STR17## the compoundsIq.13 to Iq.186, which differ from the is compounds Ia.13 to Ia.186 onlyin that R¹ is amino, R⁵ is cyano and Y is sulfur: ##STR18## thecompounds Ir.13 to Ir.183, which differ from the compounds Ia.13 toIa.183 only in that Y is --So-- and R⁵ is cyano: ##STR19## the compoundsIs.13 to Is.183, which differ from the compounds Ia.13 to Ia.183 only inthat R¹ is amino, R⁵ is cyano and Y is --SO--: ##STR20## the compoundsIt.13 to It.183, which differ from the compounds Ia.13 to Ia.183 only inthat R⁵ is cyano and Y is --SO₂ --: ##STR21## the compounds Iu.13 toIu.183, which differ from the compounds Ia.13 to Ia.183 only in that R¹is amino, R⁵ is cyano and Y is --SO₂ --: ##STR22##

The substituted benzothiazoles of the formula I are obtainable byvarious methods, for example by one of the following processes:

Process A)

Reaction of a substituted benzothiazole I in which R¹ is hydrogen with acompound II in a manner known per se: ##STR23##

L¹ is a conventional leaving group, such as halogen, preferablychlorine, bromine or iodine, (halo)alkylsulfonyloxy, preferablymethylsulfonyloxy or trifluoromethylsulfonyloxy, arylsulfonyloxy,preferably toluenesulfonyloxy, or alkoxysulfonyloxy, preferablymethoxysulfonyloxy or ethoxysulfonyloxy.

The reaction is usually carried out in an inert organic solvent, forexample in a protic solvent, such as the lower alcohols, preferablymethanol or ethanol, if desired as a mixture with water, or in anaprotic solvent, for example in an aliphatic or cyclic ether, such asmethyl tert-butyl ether, 1,2-dimethoxyethane, tetrahydrofuran anddioxane, in an aliphatic ketone, such as acetone, diethyl ketone orethyl methyl ketone, in an amide, such as dimethylformamide orN-methylpyrrolidone, in a sulfoxide, such as dimethyl sulfoxide, in aurea, such as tetramethylurea or1,3-dimethyltetrahydro-2(1H)-pyrimidinone, in a carboxylic ester, suchas ethyl acetate, or in a halogenated aliphatic or aromatic hydrocarbon,such as dichloromethane, dichloroethane, chlorobenzene or adichlorobenzene.

If desired, the reaction may be carried out in the presence of a base,both inorganic bases, for example carbonates, such as sodium carbonateand potassium carbonate, bicarbonates, such as sodium bicarbonate andpotassium bicarbonate, or alkali metal hydrides, such as sodium hydrideand potassium hydride, and organic bases, for example amines, such astriethylamine, pyridine and N,N-diethylaniline, or alkali metalalcoholates, such as sodium methylate, sodium ethylate and potassiumtert-butylate, being suitable.

The amount of base and alkylating agent II is in each case preferablyfrom 0.5 times to twice the molar amount, based on the amount ofstarting compound I (where R¹ is hydrogen). In general, the reactiontemperature is from 0° C. to the boiling point of the reaction mixture,in particular from 0° to 60° C.

In a preferred process variant, the salt of I, which salt is obtainedfrom the cyclization of IV where R¹ is H or V where R¹ is H according toprocess G), is alkylated, without isolation from the reactionmixture--which may also contain excess base, eg. sodium hydride, sodiumalcoholate or sodium carbonate.

Unless they can be prepared directly by the cyclization under basicconditions, described as method G), the salts of those compounds I inwhich R¹ is hydrogen can also be obtained in a manner known per se fromthe products of methods D) to I). For this purpose, for example, thesubstituted benzothiazole I in which R¹ is hydrogen is added to theaqueous solution of an inorganic or organic base. Salt formation thenusually takes place at a sufficient rate at as low as from 20° to 25° C.

It is particularly advantageous to prepare the sodium salt by dissolvingthe substituted benzothiazole I, where R¹ is hydrogen, in an aqueoussodium hydroxide solution at from 20° to 25° C., about equivalentamounts of benzothiazole I (where R¹ is H) and sodium hydroxide beingused. The corresponding salt of the benzothiazole I can then beisolated, for example by precipitation with a suitable inert solvent orby evaporating off the solvent.

Salts of the substituted benzothiazoles I whose metal ion is not analkali metal ion can usually be prepared by double decomposition of thecorresponding alkali metal salt in aqueous solution, as can ammonium,phosphonium, sulfonium and sulfoxonium salts by means of ammonia orphosphonium, sulfonium or sulfoxonium hydroxides. For example,benzothiazole metal salts which are insoluble in water can be preparedin this manner.

Process B)

Reaction of a substituted benzothiazole of the formula I, where R¹ ishydrogen, with an electrophilic aminating reagent in the presence of abase: ##STR24##

2,4-Dinitrophenoxyamine has proven particularly useful to date as anaminating reagent, but, for example, hydroxylamine-O-sulfonic acid(HOSA) may also be used and is known as an aminating reagent in theliterature (cf. for example E. Hofer et al., Synthesis 1983, 466; W.Friedrichsen et al., Heterocycles 20 (1983) 1271; H. Hart et al.,Tetrahedron Lett. 25 (1984) 2073; B. Vercek et al., Monatsh. Chem. 114(1983) 789; G. Sosnousky et al., Z. Naturforsch. 38 (1983) 884; R. S.Atkinson et al., J. Chem. Soc. Perkin Trans. 1987, 2787).

The amination can be carried out in a manner known per se (cf. forexample T. Sheradsky, Tetrahedron Lett. 1968, 1909; M. P. Wentland etal., J. Med. Chem. 27 (1984) 1103 and in particular EP-A 240 194, EP-A476 697 and EP-A 517 181, where the amination of uracils is described).

The reaction is usually carried out in a polar solvent, for example indimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide or in ethylacetate, which has to date proven particularly suitable.

Examples of suitable bases are alkali metal carbonates, such aspotassium carbonate, alkali metal alcoholates, such as sodium methylateand potassium tert-butylate, and alkali metal hydrides, such as sodiumhydride.

The amount of base and aminating agent is in each case preferably from0.5 times to twice the molar amount, based on the amount of startingcompound.

Process C)

Sulfurization of a substituted benzothiazole of the formula I, where X²is oxygen: ##STR25##

The sulfurization is carried out, as a rule, in an inert solvent ordiluent, for example in an aromatic hydrocarbon, such as toluene or oneof the xylenes, in an ether, such as diethyl ether, 1,2-dimethoxyethaneand tetrahydrofuran, or in an organic amine, such as pyridine.

Particularly suitable sulfurization reagents are phosphorus(V) sulfideand 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-dithione(Lawesson's reagent).

From 1 to 5 times the molar amount, based on the starting compound to besulfurized, is usually sufficient for a substantially complete reaction.

The reaction temperature is usually from 20° to 200° C., preferably from40° C. to the boiling point of the reaction mixture.

Process D)

Reaction of a substituted benzothiazole I in which --YR⁶ is chlorine,bromine, alkylsulfonyl or haloalkylsulfonyl in a manner known per sewith an alcohol or mercaptan III in the presence of a base: ##STR26##

Reaction is advantageously carried out in an inert solvent, for examplein an ether, such as diethyl ether, methyl-tert-butyl ether,dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran ordioxane, a ketone, such as acetone, diethyl ketone, ethyl methyl ketoneor cyclohexanone, a dipolar aprotic solvent, such as acetonitrile,dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide, a proticsolvent, such as methanol or ethanol, an aromatic hydrocarbon which ifdesired may be halogenated, such as benzene, chlorobenzene or1,2-dichlorobenzene, a heteroaromatic solvent, such as pyridine orquinoline, or a mixture of such solvents. Tetrahydrofuran, acetone,diethyl ketone and dimethylformamide are preferred.

The bases used here may be, for example, the hydroxides, hydrides,alkoxides, carbonates or bicarbonates of alkali metal and alkaline earthmetal cations, tertiary aliphatic amines, such as triethylamine,N-methylmorpholine and N-ethyl-N,N-diisopropylamine, bi- and tricyclicamines, such as diazabicycloundecane (DBU) and diazabicyclooctane(DABCO), or aromatic nitrogen bases, such as pyridine,4-dimethylaminopyridine and quinoline. Combinations of different basesare also suitable. Preferred bases are sodium hydride, sodium hydroxide,sodium carbonate, potassium carbonate, sodium methylate, sodium ethylateand potassium tert-butylate.

The starting materials are usually used in roughly stoichiometricamounts, but an excess of one or other component may also beadvantageous with regard to the procedure or for as complete conversionas possible of the starting compound I (X¹ and X² ═O; --YR⁶ ═Cl, Br,--SO₂ -alkyl or --SO₂ -haloalkyl).

The molar ratio of alcohol or mercaptan III to base is in general from1:1 to 1:3.

The concentration of the starting materials in the solvent is usuallyfrom 0.1 to 5.0 mol/l.

The reaction can be carried out at from 0° C. to the reflux temperatureof the respective solvent (mixture).

Process E)

Oxidation of a substituted benzothiazole I in which Y is sulfur to giveI where Y is --SO-- in a manner known per se (cf. for exampleHouben-Weyl, Methoden der Organischen Chemie, Georg Thieme VerlagStuttgart, vol. E 11/1, 1985, page 702 et seq., vol. IX, 4th edition,1955, page 211): ##STR27##

Suitable oxidizing agents are, for example, hydrogen peroxide, organicperoxides, such as peroxyacetic acid, peroxytrifluoroacetic acid,m-chloroperbenzoic acid, tert-butyl hydroperoxide and tert-butylhypochlorite, and inorganic compounds, such as sodium metaiodate,chromic acid and nitric acid.

Depending on the oxidizing agent, the reaction is usually carried out inan organic acid, such as acetic acid or trichloroacetic acid, in achlorinated hydrocarbon, such as methylene chloride, chloroform or1,2-dichloroethane, in an aromatic hydrocarbon, such as benzene,chlorobenzene or toluene, or in a protic solvent, such as methanol orethanol. Mixtures of the stated solvents are also suitable.

The reaction temperature is in general from -30° C. to the boiling pointof the respective reaction mixture, the lower temperature range usuallybeing preferred.

The starting compound and oxidizing agent are advantageously used in aroughly stoichiometric ratio, but one or other component may also beemployed in excess.

Process F)

Oxidation of a substituted benzothiazole I in which Y is sulfur or--SO-- to give I where Y is --SO₂ -- in a manner known per se (cf. forexample Houben-Weyl, Methoden der Organischen Chemie, Georg ThiemeVerlag Stuttgart, vol. E 11/2, 1985, page 1132 et seq., and vol. IX, 4thedition, 1955, page 222 et seq.): ##STR28##

Suitable oxidizing agents are, for example, hydrogen peroxide, organicperoxides, such as peroxyacetic acid, peroxytrifluoroacetic acid andm-chloroperbenzoic acid, and inorganic oxidizing agents, such aspotassium permanganate. The presence of a catalyst, for exampletungstate, may promote the reaction.

As a rule, the reaction is carried out in an inert solvent; depending onthe oxidizing agent, for example, organic acids, such as acetic acid andpropionic acid, chlorinated hydrocarbons, such as methylene chloride,chloroform and 1,2-dichloroethane, aromatic hydrocarbons andhalohydrocarbons, such as benzene, chlorobenzene and toluene, and watermay be used. Mixtures of the stated solvents are also suitable.

The reaction is usually carried out from -30° C. to the boiling point ofthe respective reaction mixture, preferably from 10° C. to the boilingpoint.

The starting compound I where Y is S or SO and the oxidizing agent areadvantageously used in roughly stoichiometric amounts. However, anexcess of oxidizing agent may be advisable for optimizing the conversionof starting compounds.

Process G)

Cyclization of an enamine ester of the formula IV or of an enaminecarboxylate of the formula V in the presence of a base: ##STR29##

L² is low molecular weight alkyl, preferably C₁ -C₄ -alkyl, or phenyl.

As a rule, the cyclization is carried out in an inert organic solvent ordiluent which is aprotic, for example in an aliphatic or cyclic ether,such as 1,2-dimethoxyethane, tetrahydrofuran or dioxane, in an aromatic,such as benzene or toluene, or in a polar solvent, such asdimethylformamide or dimethyl sulfoxide. Mixtures of polar solvent and ahydrocarbon, such as n-hexane, are also suitable. Depending on thestarting compound, water may also be used as a diluent.

Preferred bases are alkali metal alcoholates, in particular the sodiumalcoholates, alkali metal hydroxides, in particular sodium hydroxide andpotassium hydroxide, alkali metal carbonates, in particular sodiumcarbonate and potassium carbonate, and metal hydrides, in particularsodium hydride. Where sodium hydride is used as the base, it has provenadvantageous to carry out the reaction in an aliphatic or cyclic ether,in dimethylformamide or in dimethyl sulfoxide.

From 0.5 times to twice the molar amount, based on the amount of IV orV, of base is usually sufficient for carrying out the reactionsuccessfully.

In general, the reaction temperature is from -78° C. to the boilingpoint of the respective reaction mixture, in particular from -60° to 60°C.

If R¹ is hydrogen in the formula IV or V, the product is obtained as ametal salt, the metal corresponding to the cation of the base used. Thesalt can be isolated and purified in a manner known per se or, ifdesired, converted into the free compound I, where R¹ is hydrogen, bymeans of an acid.

Process H)

Conversion of a 2-aminobenzothiazole of the formula VI into compounds ofthe formula I where --YR⁶ is halogen, cyano, thiocyanato or cyanato bythe Sandmeyer method or a variant thereof: ##STR30##

In this type of reaction, the 2-aminobenzothiazole VI is first convertedinto a diazonium salt, this being advantageously effected in a mannerknown per se by reacting the 2-aminobenzothiazole VI with a nitrite,such as sodium nitrite or potassium nitrite, in an aqueous acidsolution--for example in aqueous hydrochloric acid, hydrobromic acid orsulfuric acid.

The diazonium salt thus obtained can then be reacted, without furtherpurification, with a corresponding acid HYR⁶, such as hydrochloric acidor hydrobromic acid, or with a corresponding metal salt of HYR⁶, such aslithium, sodium or potassium chloride, lithium, sodium or potassiumbromide, lithium, sodium or potassium cyanide or lithium, sodium orpotassium thiocyanate, in the presence of a transition metal catalyst,in particular of a copper(I) salt, such as copper(I) chloride, copper(I)bromide, copper(I) cyanide, copper(I) thiocyanate or copper(I) cyanate.

A further possibility for the preparation of the diazonium salt of thebenzothiazole VI is to react VI with an ester of nitrous acid, such astert-butyl nitrite or isopropyl nitrite, in an anhydrous system--forexample in glacial acetic acid which contains hydrogen chloride, or indioxane, absolute ethanol, tetrahydrofuran, acetonitrile or acetone. Inthis case, the diazotization can take place in the presence of atransition metal catalyst and of the corresponding metal salt of --YR⁶,as described above.

The reaction temperature is usually from -30° to 80° C.

Usually, the components of the diazotization reaction are used inroughly stoichiometric amounts, but an excess of one of the componentsmay also be advantageous, for example for achieving as completeconversion as possible of one of the other components.

The transition metal catalyst may be used in less than thestoichiometric amount, in a roughly equimolar amount or in excess, andthe acids and the metal salts may be used either in roughly equimolaramounts or, preferably, in a large excess.

Process I)

conversion of a 2-aminobenzothiazole of the formula VI into compounds ofthe formula I where Y is sulfur by mercapto dediazotization: ##STR31##

For this purpose, the 2-aminobenzothiazole VI is converted into thecorresponding diazonium salt of the benzothiazole in an anhydroussystem--for example an ether, such as dioxane or tetrahydrofuran, anitrile, such as acetonitrile, or a halohydrocarbon, such as methylenechloride or 1,2-dichloroethane--with an ester of nitrous acid, such astert-butyl nitrite or isopropyl nitrite. Said diazonium salt is thenreacted with the corresponding disulfide R⁶ --SS--R⁶. However, thediazotization itself may also be carried out in the presence of thedisulfide.

The reaction is usually carried out at from -30° to 80° C.

The reactants are advantageously used in roughly stoichiometric amounts,unless an excess of one or more of the components is advisable, forexample to achieve as complete conversion as possible of VI.

Substituted benzothiazoles of the formula I having one or more centersof chirality are usually obtained as enantiomer or diastereomermixtures, which, if desired, may be separated into the substantiallypure isomers by the conventional methods, for example by means ofcrystallization or chromatography over an optically active adsorbate.Pure optically active isomers can also be prepared, for example, fromcorresponding optically active starting materials.

Those substituted benzothiazoles of the formula I in which R¹ ishydrogen can be converted into their salts in a manner known per se (inthis context, cf. the statements under process A)).

The enamine esters of the formula IV are novel. Their preparation can becarried out by methods known per se, for example by one of the followingprocesses:

Process K)

Reaction of a β-ketocarboxylic ester VII with a urea VIII: ##STR32##

L² is low molecular weight alkyl, preferably C₁ -C₄ -alkyl, or phenyl.

The reaction was preferably carried out under essentially anhydrousconditions in an inert solvent or diluent, particularly preferably inthe presence of an acidic or basic catalyst.

Particularly suitable solvents or diluents are organic solvents capableof forming an azeotropic mixture with water, for example aromatics, suchas benzene, toluene and o-, m- and p-xylene, halogenated hydrocarbons,such as methylene chloride, chloroform, carbon tetrachloride andchlorobenzene, aliphatic and cyclic ethers, such as 1,2-dimethoxyethane,tetrahydrofuran and dioxane, and cyclohexane, as well as alcohols, suchas methanol and ethanol.

Preferred acidic catalysts are strong mineral acids, such as sulfuricacid and hydrochloric acid, phosphorus-containing acids, such asorthophosphoric acid and polyphosphoric acid, organic acids, such asp-toluenesulfonic acid, and acidic cation exchangers, such as Amberlyst15 (from Fluka).

Suitable basic catalysts are, for example, alkali metal hydrides, suchas sodium hydride, and particularly preferably alkali metal alcoholates,such as sodium methylate and ethylate.

Advantageously, VIII and the β-ketocarboxylic esters VII are used inroughly stoichiometric amounts, or the reaction is carried out with aslight excess, up to about 10 mol %, of one or other component.

From 0.5 to 2 mol %, based on the amount of one of the startingcompounds, of catalyst are usually sufficient.

In general, the reaction is carried out at from 60° to 120° C., or, forrapid removal of water formed, preferably at the boiling point of thereaction mixture.

Process L)

Reaction of an enol ether IX with a urea VIII: ##STR33##

L² and L³ are each low molecular weight alkyl, preferably C₁ -C₄ -alkyl,or phenyl.

The reaction is preferably carried out in an inert, water-miscible,organic solvent, for example an aliphatic or cyclic ether, such as1,2-dimethoxyethane, tetrahydrofuran or dioxane, or a lower alcohol, inparticular ethanol, the reaction temperature usually being from 50° to100° C., preferably at the boiling point of the reaction mixture.

However, the reaction can also be carried out in an aromatic diluent,such as benzene, toluene or o-, m- or p-xylene, the addition of eitheran acidic catalyst, such as hydrochloric acid or p-toluenesulfonic acid,or a base, for example an alkali metal alcoholate, such as sodiummethylate or sodium ethylate, being advisable in this case. In thisprocess variant, too, the reaction temperature is usually from 50° to100° C., preferably from 60° to 80° C.

The information provided for method K) is applicable with regard to theratios.

Process M)

Reaction of an enaminoester X with an isocyanate XI: ##STR34##

L² is lower molecular weight alkyl, preferably C₁ -C₄ -alkyl, or phenyl.

The reaction is advantageously carried out in the presence of anessentially anhydrous aprotic organic solvent or diluent, for example analiphatic or cyclic ether, such as diethyl ether, 1,2-dimethoxyethane,tetrahydrofuran or dioxane, an aliphatic or aromatic hydrocarbon, suchas n-hexane, benzene, toluene or o-, m- or p-xylene, a halogenated,aliphatic hydrocarbon, such as methylene chloride, chloroform, carbontetrachloride, 1,2-dichloroethane or chlorobenzene, an aprotic, polarsolvent, such as dimethylformamide, hexamethylphosphorotriamide ordimethyl sulfoxide, or a mixture of the stated solvents.

If desired, the reaction may also be carried out in the presence of ametal hydride base, such as sodium hydride or potassium hydride, or anorganic tertiary base, such as triethylamine or pyridine, and theorganic base may simultaneously serve as the solvent.

The starting materials are advantageously used in stoichiometric amountsor the reaction is carried out with a slight excess, up to about 10 mol%, of one or other component. If the reaction is carried out in theabsence of a solvent and in the presence of an organic base, the latteris present in a relatively large excess.

The reaction temperature is preferably from -80° to 50° C., inparticular from -60° to 30° C.

In a particularly preferred embodiment, the enaminoester IV obtained isreacted directly (ie. in situ) with excess base according to process G)to give the corresponding desired product I.

Process N)

Reaction of an enaminoester X with a urethane XII: ##STR35##

L² and L⁴, independently of one another, are each low molecular weightalkyl, preferably C₁ -C₄ -alkyl, or phenyl.

This reaction is advantageously carried out in an aprotic, polar solventor diluent, such as dimethylformamide, 2-butanone, dimethyl sulfoxide oracetonitrile, and advantageously in the presence of a base, for exampleof an alkali metal alcoholate or alkaline earth metal alcoholate, inparticular of a sodium alcoholate, such as sodium methylate, an alkalimetal carbonate or alkaline earth metal carbonate, in particular sodiumcarbonate, or an alkali metal hydride, such as lithium hydride or sodiumhydride.

The molar amount or twice the molar amount, based on the amount of X orXII, of base is usually sufficient.

The reaction temperature is in general from 80° to 180° C., preferablythe boiling point of the reaction mixture.

The information provided for method K) is applicable with regard to theratios of the starting compounds.

In a particularly preferred embodiment, a sodium alcoholate is used asthe base, and the alcohol formed in the course of the reaction iscontinuously distilled off. The enaminoesters IV prepared in this mannercan, without isolation from the reaction mixture, be cyclized accordingto process G) to give a salt of the substituted benzothiazoles I (whereR¹ is H).

Process O)

Reaction of an isocyanate XIII with an aniline derivative XIV: ##STR36##

L² is low molecular weight alkyl, preferably C₁ -C₄ -alkyl, or phenyl.

This reaction is advantageously carried out in an essentially anhydrous,aprotic, organic solvent or diluent, for example in the presence of analiphatic or cyclic ether, such as diethyl ether, 1,2-dimethoxyethane,tetrahydrofuran or dioxane, an aliphatic or aromatic hydrocarbon, suchas n-hexane, benzene, toluene or o-, m- or p-xylene, a halogenated,aliphatic hydrocarbon, such as methylene chloride, chloroform, carbontetrachloride, 1,2-dichloroethane or chlorobenzene, an aprotic, polarsolvent, such as dimethylformamide, hexamethylphos- phorotriamide ordimethyl sulfoxide, or a mixture of the stated solvents.

If desired, the reaction may be carried out in the presence of a metalhydride base, such as sodium hydride or potassium hydride, an alkalimetal alcoholate or alkaline earth metal alcoholate, such as sodiummethylate, sodium ethylate or potassium tert-butylate, or an organicnitrogen base, such as triethylamine or pyridine, and the organic basemay simultaneously serve as the solvent.

Starting materials are advantageously used in roughly stoichiometricamounts, or one of the components is used in an excess of up to about 20mol %. If the reaction is carried out in the absence of a solvent and inthe presence of an organic base, the latter is advantageously present inan even larger excess.

The reaction temperature is in general from -80° to 150° C., preferablyfrom -30° C. to the boiling point of the respective reaction mixture.

The enaminocarboxylates of the formula V are also novel; they too can beprepared in a manner known per se, for example by reacting an amide XVwith a urethane XVI according to process P): ##STR37##

L² is low molecular weight alkyl, preferably C₁ -C₄ -alkyl, or phenyl.

The reaction is advantageously carried out in a substantially anhydroussolvent/diluent at atmospheric pressure, particularly preferably in thepresence of an acidic catalyst.

For the preparation of enaminocarboxylates V where R¹ is amino, it isadvisable to use compounds XVI having a protected amino group (forexample as hydrazone).

Particularly suitable solvents/diluents are organic liquids capable offorming an azeotropic mixture with water, for example aromatics, such asbenzene, toluene and o-, m- or p-xylene, and halogenated hydrocarbons,such as carbon tetrachloride and chlorobenzene.

Particularly suitable catalysts are strong mineral acids, such assulfuric acid, organic acids, such as p-toluenesulfonic acid,phosphorus-containing acids, such as orthophosphoric acid andpolyphosphoric acid, and acidic cation exchangers, such as Amberlyst 15(from Fluka).

In general, a reaction temperature of from about 70° to 150° C. issufficient; however, for rapid removal of the water of reaction formed,the reaction is advantageously carried out at the boiling point of therespective reaction mixture.

XV and XVI are usually used in roughly stoichiometric amounts; XVI ispreferably used in a slight excess of up to about 20 mol %.

The amide XV can be prepared as follows:

Q): ##STR38##

The reaction is preferably carried out in an anhydrous inert aproticsolvent, for example in a halogenated hydrocarbon, such as methylenechloride, chloroform, carbon tetrachloride or chlorobenzene, an aromatichydrocarbon, such as benzene, toluene or o-, m- or p-xylene, or analiphatic or cyclic ether, such as diethyl ether, dibutyl ether,1,2-dimethoxyethane, tetrahydrofuran or dioxane.

The reaction temperature is in general from about 70° to 140° C., inparticular from 100° to 120° C.

XVII and XIV are usually used in roughly stoichiometric amounts, or oneof the components is used in an excess of up to about 10 mol %.

R): ##STR39##

The aminolysis of VII with XIV can be carried out in the absence of asolvent (cf. for example J. Chem. Soc. Dyes Col. 42 (1926), 81); Ber. 64(1931), 970; Org. Synth. Coll. IV (1963), 80; J. Am. Chem. Soc. 70(1948), 2402) or in an inert anhydrous solvent/diluent, in particular inan aprotic solvent, for example an aromatic, such as toluene or one ofthe xylenes, or a halogenated aromatic, such as chlorobenzene.

Here, it is advisable to carry out the reaction in the presence of abasic catalyst, for example a relatively high-boiling amine (cf. forexample Helv. Chim. Acta 11 (1928), 779, and U.S. Pat. No. 2,416,738) orpyridine.

The reaction temperature is preferably from about 130° to 160° C.

The starting compounds are advantageously reacted in roughlystoichiometric amounts, or a slight excess, up to about 10 mol %, of oneor other of the components used. If the reaction is carried out in thepresence of a basic catalyst, from 0.5 to 2 mol %, based on the amountof one of the starting materials, of the catalyst are usuallysufficient.

The starting compounds stated for the individual processes are eitherknown or are obtainable in a manner known per se or by a process similarto one of the processes described.

The isocyanates XI and the aniline derivatives XIV are novel if Y is--SO-- or --SO₂ --. Preferred among these are those compounds XI and XIVin which R⁴, R⁵ and/or R⁶ have the following meanings:

R⁴ is hydrogen, fluorine, chlorine or bromine;

R⁵ is cyano or halogen, in particular cyano, fluorine, chlorine orbromine;

R⁶ is C₁ -C₆ -haloalkyl, C₃ -C₆ -alkenyl, C₃ `C₆ -alkynyl or C₁ -C₆-alkyl which may be unsubstituted or substituted by cyano, C₁ -C₆-alkoxy, (C₁ -C₆ -alkoxy)carbonyl, (C₁ -C₆ -alkyl)carbonyloxy or C₁ -C₆-haloalkoxy.

Particularly preferred compounds XI and XIV are those in which R⁶ is oneof the radicals from the group 6.101-6.149 (Table 3):

                  TABLE 3    ______________________________________    No.            R.sup.6    ______________________________________    6.101          CH.sub.2 Cl    6.102          CH.sub.2 F    6.103          CHF.sub.2    6.104          CF.sub.3    6.105          CClF.sub.2    6.106          CCl.sub.2 F    6.107          CH.sub.2 CH.sub.2 Cl    6.108          CH.sub.2 CH.sub.2 F    6.109          CH.sub.2 CH.sub.2 Br    6.110          CH.sub.2 CH.sub.2 I    6.111          CH.sub.2 CF.sub.3    6.112          CF.sub.2 CF.sub.3    6.113          CH.sub.2 CH═CH.sub.2    6.114          CH(CH.sub.3)CH═CH.sub.2    6.115          CH.sub.2 CH═CHCH.sub.3    6.116          CH(CH.sub.3)CH═CH--CH.sub.3    6.117          CH.sub.2 C.tbd.CH    6.118          CH(CH.sub.3)C.tbd.CH    6.119          CH.sub.3    6.120          CH.sub.2 CH.sub.3    6.121          n-C.sub.3 H.sub.7    6.122          i-C.sub.3 H.sub.7    6.123          n-C.sub.4 H.sub.9    6.124          i-C.sub.4 H.sub.9    6.125          s-C.sub.4 H.sub.9    6.126          t-C.sub.4 H.sub.9    6.127          n-C.sub.5 H.sub.11    6.128          n-C.sub.6 H.sub.13    6.129          CH.sub.2 CN    6.130          CH(CH.sub.3)CN    6.131          CH.sub.2 CH.sub.2 CN    6.132          CH(CH.sub.3)CH.sub.2 CN    6.133          CH.sub.2 CH.sub.2 OCH.sub.3    6.134          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3    6.135          CH(CH.sub.3)CH.sub.2 OCH.sub.3    6.136          CH(CH.sub.3)CH.sub.2 OCH.sub.2 CH.sub.3    6.137          CH.sub.2 COOCH.sub.3    6.138          CH.sub.2 COOCH.sub.2 CH.sub.3    6.139          CH.sub.2 COOCH(CH.sub.3).sub.2    6.140          CH(CH.sub.3)COOCH.sub.3    6.141          CH(CH.sub.3)COOCH.sub.2 CH.sub.3    6.142          CH(CH.sub.3)COOCH(CH.sub.3).sub.2    6.143          CH.sub.2 CH.sub.2 COOCH.sub.3    6.144          CH.sub.2 CH.sub.2 COOCH.sub.2 CH.sub.3    6.145          CH(CH.sub.2 CH.sub.3)COOCH.sub.3    6.146          CH(CH.sub.2 CH.sub.3)COOCH.sub.2 CH.sub.3    6.147          CH.sub.2 CH.sub.2 OCOCH.sub.3    6.148          CH.sub.2 CH.sub.2 OCHF.sub.2    6.149          CH.sub.2 CH.sub.2 OCH.sub.2 CF.sub.3    ______________________________________

The aniline derivatives XIVa (= XIV where R⁵ is Cl and Y is --SO--), inparticular the compounds XIVa.1 to XIVa.188 shown in Table 4, are veryparticularly preferred:

                  TABLE 4    ______________________________________     ##STR40##    No.         R.sup.4   R.sup.6    ______________________________________    XIVa.1      H         CH.sub.3    XIVa.2      F         CH.sub.3    XIVa.3      Cl        CH.sub.3    XIVa.4      Br        CH.sub.3    XIVa.5      H         CH.sub.2 CH.sub.3    XIVa.6      F         CH.sub.2 CH.sub.3    XIVa.7      Cl        CH.sub.2 CH.sub.3    XIVa.8      Br        CH.sub.2 CH.sub.3    XIVa.9      H         CH.sub.2 CH.sub.2 CH.sub.3    XIVa.10     F         CH.sub.2 CH.sub.2 CH.sub.3    XIVa.11     Cl        CH.sub.2 CH.sub.2 CH.sub.3    XIVa.12     Br        CH.sub.2 CH.sub.2 CH.sub.3    XIVa.13     H         CH(CH.sub.3).sub.2    XIVa.14     F         CH(CH.sub.3).sub.2    XIVa.15     Cl        CH(CH.sub.3).sub.2    XIVa.16     Br        CH(CH.sub.3).sub.2    XIVa.17     H         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3    XIVa.18     F         CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3    XIVa.19     Cl        CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3    XIVa.20     Br        CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3    XIVa.21     H         CHCH(CH.sub.3).sub.2    XIVa.22     F         CHCH(CH.sub.3).sub.2    XIVa.23     Cl        CHCH(CH.sub.3).sub.2    XIVa.24     Br        CHCH(CH.sub.3).sub.2    XIVa.25     H         C(CH.sub.3).sub.3    XIVa.26     F         C(CH.sub.3).sub.3    XIVa.27     Cl        C(CH.sub.3).sub.3    XIVa.28     Br        C(CH.sub.3).sub.3    XIVa.29     H         CH(CH.sub.3)CH.sub.2 CH.sub.3    XIVa.30     F         CH(CH.sub.3)CH.sub.2 CH.sub.3    XIVa.31     Cl        CH(CH.sub.3)CH.sub.2 CH.sub.3    XIVa.32     Br        CH(CH.sub.3)CH.sub.2 CH.sub.3    XIVa.33     H         CH.sub.2 CHCH.sub.2    XIVa.34     F         CH.sub.2 CHCH.sub.2    XIVa.35     Cl        CH.sub.2 CHCH.sub.2    XIVa.36     Br        CH.sub.2 CHCH.sub.2    XIVa.37     H         CH(CH.sub.3)CHCH.sub.2    XIVa.38     F         CH(CH.sub.3)CHCH.sub.2    XIVa.39     Cl        CH(CH.sub.3)CHCH.sub.2    XIVa.40     Br        CH(CH.sub.3)CHCH.sub.2    XIVa.41     H         CH.sub.2 CCH    XIVa.42     F         CH.sub.2 CCH    XIVa.43     Cl        CH.sub.2 CCH    XIVa.44     Br        CH.sub.2 CCH    XIVa.45     H         CH(CH.sub.3)C CH    XIVa.46     F         CH(CH.sub.3)C CH    XIVa.47     Cl        CH(CH.sub.3)C CH    XIVa.48     Br        CH(CH.sub.3)C CH    XIVa.49     H         CH.sub.2 C CCH.sub.3    XIVa.50     F         CH.sub.2 C CCH.sub.3    XIVa.51     Cl        CH.sub.2 C CCH.sub.3    XIVa.52     Br        CH.sub.2 C CCH.sub.3    XIVa.53     H         CH.sub.2 Cl    XIVa.54     F         CH.sub.2 Cl    XIVa.55     Cl        CH.sub.2 Cl    XIVa.56     Br        CH.sub.2 Cl    XIVa.57     H         CH.sub.2 F    XIVa.58     F         CH.sub.2 F    XIVa.59     Cl        CH.sub.2 F    XIVa.60     Br        CH.sub.2 F    XIVa.61     H         CHF.sub.2    XIVa.62     F         CHF.sub.2    XIVa.63     Cl        CHF.sub.2    XIVa.64     Br        CHF.sub.2    XIVa.65     H         CF.sub.3    XIVa.66     F         CF.sub.3    XIVa.67     Cl        CF.sub.3    XIVa.68     Br        CF.sub.3    XIVa.69     H         CClF.sub.2    XIVa.70     F         CClF.sub.2    XIVa.71     Cl        CClF.sub.2    XIVa.72     Br        CClF.sub.2    XIVa.73     H         CCl.sub.2 F    XIVa.74     F         CCl.sub.2 F    XIVa.75     Cl        CCl.sub.2 F    XIVa.76     Br        CCl.sub.2 F    XIVa.77     H         CH.sub.2 CH.sub.2 Cl    XIVa.78     F         CH.sub.2 CH.sub.2 Cl    XIVa.79     H         CH.sub.2 CH.sub.2 Cl    XIVa.80     H         CH.sub.2 CH.sub.2 Cl    XIVa.81     H         CH.sub.2 CH.sub.2 F    XIVa.82     F         CH.sub.2 CH.sub.2 F    XIVa.83     Cl        CH.sub.2 CH.sub.2 F    XIVa.84     Br        CH.sub.2 CH.sub.2 F    XIVa.85     H         CH.sub.2 CF.sub.3    XIVa.86     F         CH.sub.2 CF.sub.3    XIVa.87     Cl        CH.sub.2 CF.sub.3    XIVa.88     Br        CH.sub.2 CF.sub.3    XIVa.89     H         CF.sub.2 CF.sub.3    XIVa.90     F         CF.sub.2 CF.sub.3    XIVa.91     Cl        CF.sub.2 CF.sub.3    XIVa.92     Br        CF.sub.2 CF.sub.3    XIVa.93     H         CH.sub.2 CN    XIVa.94     F         CH.sub.2 CN    XIVa.95     Cl        CH.sub.2 CN    XIVa.96     Br        CH.sub.2 CN    XIVa.97     H         CH(CH.sub.3)CN    XIVa.98     F         CH(CH.sub.3)CN    XIVa.99     Cl        CH(CH.sub.3)CN    XIVa.100    Br        CH(CH.sub.3)CN    XIVa.101    H         CH.sub.2 CH.sub.2 CN    XIVa.102    F         CH.sub.2 CH.sub.2 CN    XIVa.103    Cl        CH.sub.2 CH.sub.2 CN    XIVa.104    Br        CH.sub.2 CH.sub.2 CN    XIVa.105    H         CH(CH.sub.3)CH.sub.2 CN    XIVa.106    F         CH(CH.sub.3)CH.sub.2 CN    XIVa.107    Cl        CH(CH.sub.3)CH.sub.2 CN    XIVa.108    Br        CH(CH.sub.3)CH.sub.2 CN    XIVa.109    H         CH.sub.2 CH.sub.2 OCH.sub.3    XIVa.110    F         CH.sub.2 CH.sub.2 OCH.sub.3    XIVa.111    Cl        CH.sub.2 CH.sub.2 OCH.sub.3    XIVa.112    Br        CH.sub.2 CH.sub.2 OCH.sub.3    XIVa.113    H         CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3    XIVa.114    F         CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3    XIVa.115    Cl        CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3    XIVa.116    Br        CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3    XIVa.117    H         CH(CH.sub.3)CH.sub.2 OCH.sub.3    XIVa.118    F         CH(CH.sub.3)CH.sub.2 OCH.sub.3    XIVa.119    Cl        CH(CH.sub.3)CH.sub.2 OCH.sub.3    XIVa.120    Br        CH(CH.sub.3)CH.sub.2 OCH.sub.3    XIVa.121    H         CH(CH.sub.3)CH.sub.2 OCH.sub.2 CH.sub.3    XIVa.122    F         CH(CH.sub.3)CH.sub.2 OCH.sub.2 CH.sub.3    XIVa.123    Cl        CH(CH.sub.3)CH.sub.2 OCH.sub.2 CH.sub.3    XIVa.124    Br        CH(CH.sub.3)CH.sub.2 OCH.sub.2 CH.sub.3    XIVa.125    H         CH.sub.2 COOCH.sub.3    XIVa.126    F         CH.sub.2 COOCH.sub.3    XIVa.127    Cl        CH.sub.2 COOCH.sub.3    XIVa.128    Br        CH.sub.2 COOCH.sub.3    XIVa.129    H         CH.sub.2 COOCH.sub.2 CH.sub.3    XIVa.130    F         CH.sub.2 COOCH.sub.2 CH.sub.3    XIVa.131    Cl        CH.sub.2 COOCH.sub.2 CH.sub.3    XIVa.132    Br        CH.sub.2 COOCH.sub.2 CH.sub.3    XIVa.133    H         CH.sub.2 COOCH(CH.sub.3).sub.2    XIVa.134    F         CH.sub.2 COOCH(CH.sub.3).sub.2    XIVa.135    Cl        CH.sub.2 COOCH(CH.sub.3).sub.2    XIVa.136    Br        CH.sub.2 COOCH(CH.sub.3).sub.2    XIVa.137    H         CH(CH.sub.3)COOCH.sub.3    XIVa.138    F         CH(CH.sub.3)COOCH.sub.3    XIVa.139    Cl        CH(CH.sub.3)COOCH.sub.3    XIVa.140    Br        CH(CH.sub.3)COOCH.sub.3    XIVa.141    H         CH(CH.sub.3)COOCH.sub.2 CH.sub.3    XIVa.142    F         CH(CH.sub.3)COOCH.sub.2 CH.sub.3    XIVa.143    Cl        CH(CH.sub.3)COOCH.sub.2 CH.sub.3    XIVa.144    Br        CH(CH.sub.3)COOCH.sub.2 CH.sub.3    XIVa.145    H         CH.sub.2 CH.sub.2 COOCH.sub.3    XIVa.146    F         CH.sub.2 CH.sub.2 COOCH.sub.3    XIVa.147    Cl        CH.sub.2 CH.sub.2 COOCH.sub.3    XIVa.148    Br        CH.sub.2 CH.sub.2 COOCH.sub.3    XIVa.149    H         CH.sub.2 CH.sub.2 COOCH.sub.2 CH.sub.3    XIVa.150    F         CH.sub.2 CH.sub.2 COOCH.sub.2 CH.sub.3    XIVa.151    Cl        CH.sub.2 CH.sub.2 COOCH.sub.2 CH.sub.3    XIVa.152    H         CH.sub.2 CH.sub.2 COOCH.sub.2 CH.sub.3    XIVa.153    H         CH(CH.sub.2 CH.sub.3)COOCH.sub.3    XIVa.154    F         CH(CH.sub.2 CH.sub.3)COOCH.sub.3    XIVa.155    Cl        CH(CH.sub.2 CH.sub.3)COOCH.sub.3    XIVa.156    Br        CH(CH.sub.2 CH.sub.3)COOCH.sub.3    XIVa.157    H         CH(CH.sub.2 CH.sub.3)COOCH.sub.2 CH.sub.3    XIVa.158    F         CH(CH.sub.2 CH.sub.3)COOCH.sub.2 CH.sub.3    XIVa.159    Cl        CH(CH.sub.2 CH.sub.3)COOCH.sub.2 CH.sub.3    XIVa.160    Br        CH(CH.sub.2 CH.sub.3)COOCH.sub.2 CH.sub.3    XIVa.161    H         CH CH(CH.sub.3).sub.2 !COOCH.sub.3    XIVa.162    F         CH CH(CH.sub.3).sub.2 !COOCH.sub.3    XIVa.163    Cl        CH CH(CH.sub.3).sub.2 !COOCH.sub.3    XIVa.164    Br        CH CH(CH.sub.3).sub.2 !COOCH.sub.3    XIVa.165    H         CH.sub.2 CH.sub.2 OCOCH.sub.3    XIVa.166    F         CH.sub.2 CH.sub.2 OCOCH.sub.3    XIVa.167    Cl        CH.sub.2 CH.sub.2 OCOCH.sub.3    XIVa.168    Br        CH.sub.2 CH.sub.2 OCOCH.sub.3    XIVa.169    H         CH.sub.2 CH.sub.2 OCOCH.sub.2 CH.sub.3    XIVa.170    F         CH.sub.2 CH.sub.2 OCOCH.sub.2 CH.sub.3    XIVa.171    Cl        CH.sub.2 CH.sub.2 OCOCH.sub.2 CH.sub.3    XIVa.172    Br        CH.sub.2 CH.sub.2 OCOCH.sub.2 CH.sub.3    XIVa.173    H         CH(CH.sub.3)CH.sub.2 OCOCH.sub.3    XIVa.174    F         CH(CH.sub.3)CH.sub.2 OCOCH.sub.3    XIVa.175    Cl        CH(CH.sub.3)CH.sub.2 OCOCH.sub.3    XIVa.176    Br        CH(CH.sub.3)CH.sub.2 OCOCH.sub.3    XIVa.177    H         CH.sub.2 CH(CH.sub.3)OCOCH.sub.3    XIVa.178    F         CH.sub.2 CH(CH.sub.3)OCOCH.sub.3    XIVa.179    Cl        CH.sub.2 CH(CH.sub.3)OCOCH.sub.3    XIVa.180    Br        CH.sub.2 CH(CH.sub.3)OCOCH.sub.3    XIVa.181    H         CH.sub.2 CH.sub.2 OCHF.sub.3    XIVa.182    F         CH.sub.2 CH.sub.2 OCHF.sub.3    XIVa.183    Cl        CH.sub.2 CH.sub.2 OCHF.sub.3    XIVa.184    Br        CH.sub.2 CH.sub.2 OCHF.sub.3    XIVa.185    H         CH.sub.2 CH.sub.2 OCH.sub.2 CF.sub.3    XIVa.186    F         CH.sub.2 CH.sub.2 OCH.sub.2 CF.sub.3    XIVa.187    Cl        CH.sub.2 CH.sub.2 OCH.sub.2 CF.sub.3    XIVa.188    Br        CH.sub.2 CH.sub.2 OCH.sub.2 CF.sub.3    ______________________________________

Furthermore, the isocyanates XIa to XIh and the aniline derivatives XIVbto XIVh are very particularly preferred, in particular:

the compounds XIa.1-XIa.188 in which Y and R⁴ to R⁶ have the samemeanings as in the corresponding compounds XIVa.1-XIVa.188: ##STR41##the compounds XIVb.1-XIVb.188 which differ from the compoundsXIVa.1-XIVa.188 only in that Y is --SO₂ --: ##STR42## the compoundsXIb.1-XIb.188 in which Y and R⁴ to R⁶ have the same meanings as in thecorresponding compounds XIVb.1-XIVb.188: ##STR43## the compoundsXIVc.1-XIVc.188 which differ from the compounds XIVa.1-XIVa.188 only inthat R⁵ is fluorine: ##STR44## the compounds XIc.1-XIc.188 in which Yand R⁴ to R⁶ have the same meanings as in the corresponding compoundsXIVc.1-XIVc.188: ##STR45## the compounds XIVd.1-XIVd.188 which differfrom the compounds XIVa.1-XIVa.188 only in that R⁵ is fluorine and Y is--SO₂ --: ##STR46## the compounds XId.1-XId.188 in which Y and R⁴ to R⁶have the same meanings as in the corresponding compoundsXIVd.1-XIVd.188: ##STR47## the compounds XIVe.1-XIVe.188 which differfrom the compounds XIVa.1-XIVa.188 only in that R⁵ is bromine: ##STR48##the compounds XIe.1-XIe.188 in which Y and R⁴ to R⁶ have the samemeanings as in the corresponding compounds XIVe.1-XIVe.188: ##STR49##the compounds XIVf.1-XIVf.188 which differ from the compoundsXIVa.1-XIVa.188 only in that R⁵ is bromine and Y is --SO₂ --: ##STR50##the compounds XIf.1-XIf.188 in which Y and R⁴ to R⁶ have the samemeanings as in the corresponding compounds XIVf.1-XIVf.188: ##STR51##the compounds XIVg.1-XIVg.188 which differ from the compoundsXIVa.1-XIVa.188 only in that R⁵ is cyano: ##STR52## the compoundsXIg.1-XIg.188 in which Y and R⁴ to R⁶ have the same meanings as in thecorresponding compounds XIVg.1-XIVg.188: ##STR53## the compoundsXIVh.1-XIVh.188, which differ from the compounds XIVa.1-XIVa.188 only inthat R⁵ is cyano and Y is --SO₂ --: ##STR54## the compoundsXIh.1-XIh.188 in which Y and R⁴ to R⁶ have the same meanings as in thecorresponding compounds XIVh.1-XIVh.188: ##STR55##

The isocyanates XI are obtainable, for example, from the anilinederivatives XIV according to process S): ##STR56##

The process can be carried out in an inert, essentially anhydroussolvent or diluent or in the absence of a solvent, the anilinederivatives XIV preferably being reacted with phosgene, with a phosgeneequivalent, such as diphosgene, triphosgene or carbonyldiimidazole, orwith trichloromethyl chloroformate.

Particularly suitable solvents or diluents are aprotic, organicsolvents, for example aromatics, such as toluene and o-, m- andp-xylene, halogenated hydrocarbons, such as methylene chloride,chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic and cyclicethers, such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, andesters, such as ethyl acetate, and mixtures of these solvents.

The starting materials are advantageously used in roughly stoichiometricamounts, or one of the components is used in an excess of up to about200 mol %.

Depending on the aniline derivative XIV used, it may be advantageous toadd a base, such as triethylamine, for example in from 0.5 times totwice the molar amount, based on the amount of XIV.

The reaction temperature is in general from -20° C. to the refluxtemperature of the solvent or reaction mixture.

The aniline derivatives XIV are in turn obtainable in a manner known perse (cf. for example Houben-Weyl, Methoden der organischen Chemie, GeorgThieme Verlag, vol. XI/1, 4th edition 1957, page 431 et seq.), byreduction of the corresponding nitroderivatives XVIII: ##STR57##

Particularly suitable reducing agents are

elemental metals, such as iron, tin and zinc,

hydrogen in the presence of suitable catalysts, such as palladium orplatinum on carbon or Raney nickel, or

complex hydrides, such as LiAlH₄ and NaBH₄, in the presence or absenceof catalysts.

Depending on the reducing agent, suitable solvents are usuallycarboxylic acids, such as acetic acid and propionic acid, alcohols, suchas methanol and ethanol, ethers, such as diethyl ether, methyltert-butyl ether, tetrahydrofuran and dioxane, aromatics, such asbenzene and toluene, and mixtures of such solvents.

The reactions can be carried out at from -100° C. to the boiling pointof the respective reaction mixture.

The starting compounds are usually used in roughly stoichiometricamounts; in individual cases, however, an excess of up to about 10 mol %of one or other component may also be advantageous.

The compounds XI and XIV, too, may contain one or more centers ofchirality and are then usually obtained as enantiomer or diastereomermixtures. The mixtures can, if desired, be separated into thesubstantially pure isomers by the conventional methods, for example bymeans of crystallization or chromatography over an optically activeadsorbate. Pure optically active isomers can also be prepared, forexample, from corresponding optically active starting materials.

Unless stated otherwise, all processes described above areadvantageously carried out at atmospheric pressure or under theautogenous pressure of the respective reaction mixture.

The reaction mixtures are worked up, as a rule, by methods known per se,for example by dilution of the reaction mixture with water andsubsequent isolation of the desired product by means of filtration,crystallization or solvent extraction, or by removal of the solvent,partition of the residue in a mixture of water and a suitable organicsolvent and working up of the organic phase to obtain the product.

In general, the substituted benzothiazoles I can be prepared by one ofthe abovementioned synthesis methods. For economic or processengineering reasons, however, it may be more advantageous to preparesome compounds I from similar substituted benzothiazoles I, whichhowever differ in particular in the meaning of R⁶.

The compounds I and their agriculturally useful salts--both as isomermixtures and in the form of pure isomers--are suitable as herbicides.The herbicides containing them provide very effective control of plantgrowth on uncultivated areas, particularly at high application rates.They act against broad-leaved weeds and grass weeds in crops such aswheat, rice, corn, soybean and cotton, without significantly damagingthe crops. This effect occurs in particular at low application rates.

Depending on the respective application method, the compounds I or theherbicides containing them can also be used in a further number of cropsfor eliminating undesirable plants. For example, the following crops aresuitable: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagusofficinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa,Brassica napus var. napus, Brassica napus var. napobrassica, Brassicarapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Caryaillinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffeacanephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucuscarota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypiumhirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypiumvitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare,Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linumusitatissimum, Lycopersicon lycopersicum, Malus spec., Manihotesculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica),Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris,Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica,Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s.vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum,Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

In addition, the compounds I can also be used in crops which aretolerant to the action of herbicides as a result of breeding, includinggenetic engineering methods.

Substituted benzothiazoles I are also suitable for desiccating and/ordefoliating plants.

As desiccants, they are particularly suitable for drying out theabove-ground parts of crops, such as potatoes, rape, sunflower andsoybean. This permits complete mechanical harvesting of these importantcrops.

Also of commercial in terest is the facilitation of harvesting, which ispermitted by the concentrated dropping or reduction in the adhesion tothe tree in the case of citrus fruits, olives or other species andvarieties of pomes, drupes and indehiscent fruit. The same mechanism,ie. promotion of the formation of abscission tissue between fruit partor leaf part and shoot part of the plants is also important for readilycontrollable defoliation of crops, in particular cotton.

Furthermore, shortening of the time interval in which the individualcotton plants ripen leads to higher fiber quality after the harvest.

The compounds I or the herbicides containing them can be applied, forexample, in the form of directly sprayable aqueous solutions, powders,suspensions, including concentrated aqueous, oily or other suspensionsor dispersions, emulsions, oil dispersions, pastes, dusting agents,broadcasting agents or granules, by spraying, nebulizing, dusting,broadcasting or pouring. The application forms depend on the intendeduses; they should in any case ensure a very fine distribution of thenovel active ingredients.

Suitable inert assistants are essentially mineral oil fractions having amedium to high boiling point, such as kerosene and diesel oil, and coaltar oils and oils of vegetable or animal origin, aliphatic, cyclic andaromatic hydrocarbons, for example paraffins, tetrahydronaphthalene,alkylated naphthalenes and derivatives thereof, alkylated benzenes andderivatives thereof, alcohols, such as methanol, ethanol, propanol,butanol and cyclohexanol, ketones, such as cyclohexanone, strongly polarsolvents, for example amines, such as N-methylpyrrolidone, and water.

Aqueous application forms can be prepared from emulsion concentrates,suspensions, pastes, wettable powders or water-dispersible granules byadding water. For the preparation of emulsions, pastes or oildispersions, the substances, as such or dissolved in an oil or solvent,can be homogenized in water by means of wetting agents, adherents,dispersants or emulsifiers. However, it is also possible to prepareconcentrates which consist of active ingredient, wetting agents,adherents, dispersants or emulsifiers and possibly solvents or oil andwhich are suitable for dilution with water.

Suitable surfactants (adjuvants) are alkali metal, alkaline earth metaland ammonium salts of aromatic sulfonic acids, for example lignin-,phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fattyacids, alkylsulfonates and alkylarylsulfonates, alkylsulfates, laurylether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-,hepta- and octadecanols and of fatty alcohol glycol ethers, condensatesof sulfonated naphthalene and its derivatives with formaldehyde,condensates of naphthalene or of naphthalenesulfonic acids with phenoland formaldehyde, polyoxyethylene octylphenol ether, ethoxylatedisooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol ether,tributylphenyl polyglycol ether, alkylaryl polyether alcohols,isotridecyl alcohol, fatty alcohol/ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate,sorbitol esters, ligninsulfite waste liquors or methylcellulose.

Powders, broadcasting agents and dusting agents can be prepared bymixing or milling the active ingredients together with a solid carrier.

Granules, for example coated, impregnated and homogeneous granules, canbe prepared by binding the active ingredients to solid carriers. Solidcarriers are mineral earths, such as silica, silica gels, silicates,talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite,kieselguhr, calcium sulfate, magnesium sulfate, magnesium oxide, milledplastics, fertilizers, such as ammonium sulfate, ammonium phosphate,ammonium nitrate and ureas, and vegetable products, such as grain flour,bark meal, wood meal and nutshell meal, cellulosic powders and othersolid carriers.

The concentrations of the active ingredients I in the ready-to-useformulations can be varied within wide ranges. The formulationsgenerally contain from 0.001 to 98, preferably from 0.01 to 95, % byweight, of at least one active ingredient. The active ingredients areused in a purity of from 90 to 100%, preferably from 95 to 100%(according to NMR spectrum).

The following formulation examples illustrate the preparation of suchformulations:

I. 20 parts by weight of compound No. I.2 are dissolved in a mixturewhich consists of 80 parts by weight of alkylated benzene, 10 parts byweight of the adduct of from 8 to 10 mol of ethylene oxide with 1 mol ofN-monoethanololeamide, 5 parts by weight of calcium salt ofdodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40mol of ethylene oxide with 1 mol of castor oil. By pouring the solutioninto 100,000 parts by weight of water and finely distributing ittherein, an aqueous dispersion which contains 0.02% by weight of theactive ingredient is obtained.

II. 20 parts by weight of compound No. I.3 are dissolved in a mixturewhich consists of 40 parts by weight of cyclohexanone, 30 parts byweight of isobutanol, 20 parts by weight of the adduct of 7 mol ofethylene oxide with 1 mol of isooctylphenol and 10 parts by weight ofthe adduct of 40 mol of ethylene oxide with 1 mol of castor oil. Bypouring the solution into 100,000 parts by weight of water and finelydistributing it therein, an aqueous dispersion which contains 0.02% byweight of the active ingredient is obtained.

III. 20 parts by weight of active ingredient No. I.5 are dissolved in amixture which consists of 25 parts by weight of cyclohexanone, 65 partsby weight of a mineral oil fraction boiling within the range from 210°to 280° C. and 10 parts by weight of the adduct of 40 mol of ethyleneoxide with 1 mol of castor oil. By pouring the solution into 100,000parts by weight of water and finely distributing it therein, an aqueousdispersion which contains 0.02% by weight of the active ingredient isobtained.

IV. 20 parts by weight of active ingredient No. I.7 are thoroughly mixedwith 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodiumsalt of a ligninsulfonic acid obtained from a sulfite waste liquor and60 parts by weight of silica gel powder, and the mixture is milled in ahammer mill. By finely distributing the mixture in 20,000 parts byweight of water, a spray liquor which contains 0.1% by weight of theactive ingredient is obtained.

V. 3 parts by weight of active ingredient No. I.33 are mixed with 97parts by weight of finely divided kaolin. A dusting agent which contains3% by weight of the active ingredient is obtained in this manner.

VI. 20 parts by weight of active ingredient No. I.11 are thoroughlymixed with 2 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcoholpolyglycol ether, 2 parts by weight of sodium salt of aphenol/urea/formaldehyde condensate and 68 parts by weight of aparaffinic mineral oil. A stable oily dispersion is obtained.

VII. 1 part by weight of active ingredient No. I.9 is dissolved in amixture which consists of 70 parts by weight of cyclohexanone, 20 partsby weight of ethoxylated isooctylphenol and 10 parts by weight ofethoxylated castor oil. A stable emulsion concentrate is obtained.

VIII. 1 part by weight of active ingredient No. I.14 is dissolved in amixture which consists of 80 parts by weight of cyclohexanone and 20parts by weight of Wettol® EM 31 (= nonionic emulsifier based onethoxylated castor oil; BASF AG). A stable emulsion concentrate isobtained.

The active ingredients I or the herbicides can be applied by thepreemergence or postemergence method. If the active ingredients are lesstolerated by certain crops, it is possible to use application methods inwhich the herbicides are sprayed with the aid of the sprayers so thatthe leaves of the sensitive crops are as far as possible not affected,whereas the active ingredients reach the leaves of undesirable plantsgrowing underneath or the uncovered soil surface (post-directed,lay-by).

The application rates of active ingredient I are from 0.001 to 3.0,preferably from 0.01 to 1.0, kg/ha of active ingredient (a.i.),depending on the aim of control, the season, the target plants and thestage of growth.

In order to broaden the action spectrum and to achieve synergisticeffects, the substituted benzothiazoles I can be mixed with a largenumber of substances of other groups of herbicidal or growth-regulatingactive ingredients and can be applied together with these. Suitablecomponents of the mixture are, for example, 1,2,4-thiadiazoles,1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives,aminotriazoles, anilides, aryloxy-/hetaryloxyalkanoic acids and theirderivatives, benzoic acid and its derivatives, benzothiadiazinones,2-(hetaroyl/aroyl)-1,3-cyclohexanediones, hetaryl aryl ketones,benzylisoxazolidinones, meta-CF₃ -phenyl derivatives, carbamates,quinolinecarboxylic acid and its derivatives, chloroacetanilides,cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid andits derivatives, dihydrobenzofurans, dihydrofuran-3-ones,dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls,halocarboxylic acids and their derivatives, ureas, 3-phenyluracils,imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides,oxadiazoles, oxiranes, phenols, aryloxy- and hetaryloxyphenoxypropionicesters, phenylacetic acid and its derivatives, 2-phenylpropionic acidand its derivatives, pyrazoles, phenylpyrazoles, pyridazines,pyridinecarbonxylic acid and its derivatives, pyrimidyl ethers,sulfonamides, sulfonylureas, triazines, triazinones, triazolinones,triazolecarboxamides and uracils.

It may also be useful to apply the compounds I, alone or in combinationwith other herbicides, also as a mixture with further crop protectionagents, for example with pesticides or agents for controllingphytopathogenic fungi or bacteria. Also of interest is the miscibilitywith mineral salt solutions which are used for eliminating nutrient andtrace element deficiencies. Nonphytotoxic oils and oil concentrates mayalso be added.

PREPARATION EXAMPLES EXAMPLE 1 3-2,4-Dichloro-6-fluorobenzothiazol-7-yl!-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(compound I.4)

1.6 g of sodium hydride (97% strength) in 200 ml of absolutedimethylformamide were initially taken. 11.0 g of ethyl3-amino-4,4,4-trifluorobut-2-enecarboxylate were then added dropwise atfrom 0° to 5° C. Stirring was carried out for one hour at thistemperature, after which the mixture was cooled to -30° C. and 16.2 g of2,4-dichloro-6-fluoro-7-isocyanatobenzothiazole in 50 ml of absolutetetrahydrofuran were then added dropwise. The mixture was stirred forone hour at this temperature and then slowly warmed up to roomtemperature. Thereafter, ice water was added and the pH was brought to3-4 with dilute hydrochloric acid, after which the product was extractedwith ethyl acetate. The ester solution was dried and then evaporateddown.

¹ H-NMR (250 MHz; in d⁶ -dimethyl sulfoxide): δ ppm!=6.43 (s,1H), 8.06(d,1H).

EXAMPLE 2 3-4-Chloro-6-fluoro-2-propoxybenzothiazol-7-yl!-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(compound I.8)

108 ml of absolute n-propanol were added dropwise at room temperature to1.1 g of sodium hydride (97% strength) in 40 ml of absolutetetrahydrofuran. Stirring was carried out for 30 minutes, after which7.0 g of 3-2,4-dichloro-6-fluorobenzothiazol-7-yl!-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(compound I.4) were slowly added. Stirring was carried out for 12 hours,after which the solvent was distilled off at reduced pressure and theresidue was then taken up in water. 10% strength hydrochloric acid wasadded to the aqueous phase until the resulting pH was from 3 to 4. Theprecipitate formed was separated off, washed with water and then dried.Yield: 5.2 g.

¹ H-NMR (250 MHz; in d⁶ -dimethyl sulfoxide): δ ppm!=0.95 (t,3H), 1.72(sex,2H), 4.53 (t,2H), 6.46 (s,1H), 7.82 (d,1H).

EXAMPLE 3 3-4-Chloro-6-fluoro-2-propoxybenzothiazol-7-yl!-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (compound I.9)

1.7 g of methyl iodide were added dropwise at about 20° C. to a mixtureof 200 ml of absolute ethyl methyl ketone, 1.7 g of potassium carbonateand 5.0 g of 3-4-chloro-6-fluoro-2-propoxybenzothiazol-7-yl!-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(compound I.8). Stirring was carried out for 12 hours at roomtemperature, after which the insoluble components were filtered off. Theclear solution obtained was evaporated down. The residue was then takenup in water, after which the solution was neutralized with dilutehydrochloric acid. The product was then extracted with ethyl acetate.The ester phase was finally dried over sodium sulfate and thenevaporated down. The purification of the crude product thus obtained wascarried out by chromatography over silica gel (eluent: 9:1cyclohexane/methyl tert-butyl ether). Yield: 1.0 g.

¹ H-NMR (250 MHz; in CDCl₃): δ ppm!=1.04 (t,3H), 1.88 (sex,2H), 3.58(s,3H), 4.58 (t,2H), 6.39 (s,1H), 7.32 (d,1H).

EXAMPLE 43-(4-Chloro-6-fluoro-2-methylbenzothiazol-7-yl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(compound I.15)

0.5 g (20 mmol) of sodium hydride was suspended in 50 ml ofdimethylformamide, and 2.7 g (15 mmol) of methyl3-amino-4,4,4-trifluorobut-2-enoate were added while cooling with ice.After 1 hour, the mixture was cooled to -30° C. and the isocyanate frompreliminary stage 4.4, dissolved in 20 ml of tetrahydrofuran, was addedto the reaction mixture. Stirring was then carried out for 16 hours atabout 20° C. Thereafter, ice water was added to the reaction mixture,after which it was acidified with dilute hydrochloric acid. The desiredproduct was extracted with ethyl acetate, after which the organic phasewas dried over magnesium sulfate and was finally evaporated down.Purification of the crude product was effected by means of columnchromatography over silica gel (eluent: 9:1 cyclohexane/methyltert-butyl ether).

Yield: 1 g.

¹ H-NMR (250 MHz; in CDCl₃): δ ppm!=2.85 (s,3H), 6.26 (s,1H), 7.45(d,1H).

Preliminary stage 4.1

4-Chloro-6-fluoro-2-methylbenzothiazole

67 ml of a solution of methyl magnesium chloride in tetrahydrofuran (3M;0.2 mol) were added dropwise to a solution of 22 g (0.1 mol) of2,4-dichloro-6-fluorobenzothiazole and 3.3 g (5 mmol) ofdichlorobis(triphenylphosphine)nickel in 100 ml of diethyl ether. Afterstirring had been carried out for 2 hours, the mixture was poured ontosaturated aqueous ammonium chloride solution. The desired product wasextracted with diethyl ether, after which the combined organic phaseswere washed with water, dried over magnesium sulfate and finallyevaporated down. 10 g of the desired product were obtained bycrystallization from petroleum ether.

¹ H-NMR (250 MHz; in CDCl₃): δ ppm!=2.85 (s,3H), 7.24 (dd,1H), 7.41(dd,1H).

Preliminary stage 4.2

4-Chloro-6-fluoro-2-methyl-7-nitrobenzothiazole

A solution of 7 ml of concentrated nitric acid in 6 ml of concentratedsulfuric acid was added to a solution of 10 g (50 mmol) of4-chloro-6-fluoro-2-methylbenzothiazole in 35 ml of concentratedsulfuric acid. Stirring was carried out for 10 minutes, after which themixture was poured into ice water. Thereafter, the suspended desiredproduct was separated off and, for purification, was dissolved in 100 mlof 3:1 cyclohexane/ethyl acetate. After filtration over a bed of silicagel, 8 g of desired product was obtained from the remaining solution;mp.: 130° to 132° C.

Preliminary stage 4.3

7-Amino-4-chloro-6-fluoro-2-methylbenzothiazole

6 g of iron powder were added to a suspension of 8 g (32 mmol) of4-chloro-6-fluoro-2-methyl-7-nitrobenzothiazole in 100 ml of water and 9ml of concentrated hydrochloric acid, which suspension had been heatedto 80° C., after which the mixture was refluxed for 3 hours. 200 ml ofethyl acetate were then added to the reaction mixture. The solid wasfiltered off. The remaining organic phase was washed with water, driedover magnesium sulfate and finally evaporated down. Yield: 4.5 g.

¹ H-NMR (250 MHz; in CDCl₃): δ ppm!=2.85 (s,3H), 3.93 (s,2H), 7.22(d,1H).

Preliminary stage 4.4

4-Chloro-6-fluoro-7-isocyanato-2-methylbenzothiazole

A solution of 3.2 g (15 mmol) of7-amino-4-chloro-6-fluoro-2-methylbenzothiazole and 15 g (76 mmol) ofdiphosgene in 150 ml of toluene was refluxed for 6 hours. The crudeproduct obtained after evaporation was converted directly into activeingredient I.15.

EXAMPLE 53-(4-Chloro-6-fluoro-2-(methylthio)benzothiazol-7-yl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (compound I.10)

First, 4-chloro-6-fluoro-7-isocyanato-2-(methylthio)benzothiazole wasprepared by refluxing a solution of 7 g (28 mmol) of7-amino-4-chloro-6-fluoro-2-(methylthio)benzothiazole and 55 g (0.28mol) of diphosgene (200 ml of toluene for 7 hours, then adding 20 g (0.1mol) of phosgene, refluxing for a further 8 hours and finallyevaporating down.

2.7 g (15 mmol) of ethyl 3-amino-4,4,4-trifluorobut-2-enoate were thenadded to a suspension of 0.7 g (30 mmol) of sodium hydride in 50 ml ofdimethylformamide while cooling with ice. Stirring was carried out forone hour, after which the mixture was cooled to -30° C. and a solutionof the initially prepared isocyanate in 50 ml of tetrahydrofuran wasthen added to the mixture. Stirring was carried out for a further 16hours at about 20° C. After the addition of ice water, the mixture wasacidified with dilute hydrochloric acid. The product was extracted withethyl acetate. The organic phase separated off was finally dried overmagnesium sulfate and evaporated down. Yield: 4 g.

¹ H-NMR (250 MHz; in CDCl₃): δ ppm!=2.78 (s,3H), 6.22 (s,1H), 7.35(d,1H).

Preliminary stage 5.1

2-Amino-4-chloro-6-fluorobenzothiazole

30 g (0.2 mol) of 2-chloro-4-fluoroaniline were reacted similarly topreliminary stage 9.1. Yield: 19.4 g.

¹ H-NMR (400 MHz; in d⁶ -dimethyl sulfoxide): δ ppm!=7.28 (d,1H), 7.62(d,1H), 7.90 (s,2H).

Preliminary stage 5.2

4-Chloro-6-fluoro-2-(methylthio)benzothiazole

27 g (0.13 mol) of 2-amino-4-chloro-6-fluorobenzothiazole were reactedsimilarly to preliminary stage 6.1. Yield: 20 g.

¹ H-NMR (270 MHz; in CDCl₃): δ ppm!=2.80 (s,3H), 7.21 (dd,1H), 7.36(dd,1H).

Preliminary stage 5.3

4-Chloro-6-fluoro-2-methylsulfinyl-7-nitrobenzothiazole

21.8 g (93 mmol) of 4-chloro-6-fluoro-2-(methylthio)benzothiazole werereacted similarly to preliminary stage 4.2. Yield: 21.2 g.

¹ H-NMR (250 MHz; in CDCl₃): δ ppm!=3.16 (s,3H), 7.66 (d,1H).

Preliminary stage 5.4

7-Amino-4-chloro-6-fluoro-2-(methylthio)benzothiazole

19.1 g of 4-chloro-6-fluoro-2-methylsulfinyl-7-nitrobenzothiazole werereacted similarly to preliminary stage 4.3, but refluxing was carriedout for 24 hours in order to reduce both the nitro and the sulfinylgroup. Yield: 12 g.

¹ H-NMR (270 MHz; in CDCl₃): δ ppm!=2.82 (s,3H), 7.20 (d,1H).

EXAMPLE 63-(4,6-Dichloro-2-(methylthio)benzothiazol-7-yl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(compound I.20)

4.0 g (15 mmol) of 7-amino-4,6-dichloro-2-(methylthio)benzothiazole werereacted similarly to Example 5. Yield: 4.4 g.

¹ H-NMR (270 MHz; in CDCl₃): δ ppm!=2.82 (s,3H), 6.27 (s,1H), 7.66(s,1H).

Preliminary stage 6.1

4,6-Dichloro-2-(methylthio)benzothiazole

43.7 g (0.47 mol) of dimethyl disulfide and 154.5 g (1.5 mol) oftert-butyl nitrite were added to a solution of 34 g (0.16 mol) of2-amino-4,6-dichlorobenzothiazole in 1 liter of 1,2-dichloroethane.Stirring was carried out for 16 hours, followed by washing with waterand 10% strength sodium hydroxide solution, drying over magnesiumsulfate and evaporating down.

Yield: 34 g; mp.: 108° to 110° C.

Preliminary stage 6.2

4,6-Dichloro-2-methylthio-7-nitrobenzothiazole

23 g (92 mmol) of 4,6-dichloro-2-(methylthio)benzothiazole were reactedsimilarly to preliminary stage 4.2. However, purification of the crudeproduct was carried out by means of silica gel chromatography (eluent:4:1 cyclohexane/ethyl acetate). Yield: 23 g; mp.: 130° to 132° C.

Preliminary stage 6.3

7-Amino-4,6-dichloro-2-(methylthio)benzothiazole

5.5 g (19 mmol) of 4,6-dichloro-2-methylthio-7-nitrobenzothiazole werereacted similarly to preliminary stage 4.3. Yield: 5.0 g.

¹ H-NMR (270 MHz; in CDCl₃): δ ppm!=2.84 (s,3H), 4.15 (s,2H), 7.39(s,1H).

EXAMPLE 73-(4-Chloro-6-fluoro-2-(methylsulfinyl)benzothiazol-7-yl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(compound I.22) and3-(4-chloro-6-fluoro-2-(methylsulfonyl)-benzothiazol-7-yl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(compound I.23)

0.6 g (1.7 mmol) of 50% strength m-chloroperbenzoic acid was added at 0°C. to a solution of 0.7 g (1.6 mmol) of3-(4-chloro-6-fluoro-2-(methylthio)benzothiazol-7-yl)-l-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedionein 50 ml of dichloromethane. Stirring was carried out for 16 hours,followed by washing in succession with water, saturated aqueous sodiumthiosulfate solution, water, 10% strength sodium hydroxide solution andwater. This was followed by drying over magnesium sulfate and finally byevaporating down. The two products were separated by silica gelchromatography (eluent: 4:1 cyclohexane/methyl tert-butyl ether).

Yield: first 50 mg of compound I.23, then 0.12 g of compound I.22.

EXAMPLE 83-(4,6-Dichloro-2-methylbenzothiazol-7-yl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(compound I.24)

3.5 g (15 mmol) of 7-amino-4,6-dichloro-2-methylbenzothiazole werereacted similarly to Example 5. Yield: 3 g.

¹ H-NMR (270 MHz; in d⁶ -dimethyl sulfoxide): δ ppm!=2.86 (s,3H), 6.58(s,1H), 8.04 (s,1H).

Preliminary stage 8.1

4,6-Dichloro-2-methyl-7-nitrobenzothiazole

6.9 g (32 mmol) of 4,6-dichloro-2-methylbenzothiazole were reactedsimilarly to preliminary stage 4.2. Yield: 8.3 g.

¹ H-NMR (270 MHz; in CDCl₃): δ ppm!=2.91 (s,3H), 7.73 (s,1H).

Preliminary stage 8.2

7-Amino-4,6-dichloro-2-methylbenzothiazole

8.3 g (32 mmol) of 4,6-dichloro-2-methyl-7-nitrobenzothiazole werereacted similarly to preliminary stage 4.3. Yield: 3.5 g.

¹ H-NMR (270 MHz; in d⁶ -dimethyl sulfoxide): δ ppm!=2.81 (s,3H), 5.99(s,2H), 7.47 (s,1H).

EXAMPLE 93-(4,6-Dichlorobenzothiazol-7-yl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(compound I.26)

3 g of desired product were obtained from 3.0 g (14 mmol) of7-amino-4,6-dichlorobenzothiazole in the manner described in Example 5.

¹ H-NMR (270 MHz; in d⁶ -dimethyl sulfoxide): δ ppm!=6.56 (s,1H), 8.12(s,1H), 9.57 (s,1H).

Preliminary stage 9.1

2-Amino-4,6-dichlorobenzothiazole

197 g (1.23 mol) of bromine were slowly added dropwise, while coolingwith ice, to a solution of 200 g (1.23 mol) of 2,4-dichloroaniline and200 g (2.46 mol) of sodium thiocyanate in 1.5 1 of glacial acetic acid.Stirring was carried out for 16 hours at about 20° C., after which thesolid was separated off and washed with 10% strength sodium hydroxidesolution and water.

Yield: 205 g.

¹ H-NMR (270 MHz; in d⁶ -dimethyl sulfoxide): δ ppm!=7.39 (d,1H), 7.80(d,1H), 8.00 (s,2H).

Preliminary stage 9.2

2-Bromo-4,6-dichlorobenzothiazole

35 g (0.24 mol) of copper(I) bromide and 126 g (1.23 mol) of sodiumbromide were added to a solution of 27 g (0.12 mol) of2-amino-4,6-dichlorobenzothiazole in 0.5 1 of acetonitrile, and 16.5 g(0.16 mol) of tert-butyl nitrite were then added dropwise. Stirring wascarried out for 16 hours, after which the reaction mixture was acidifiedwith 10% strength hydrochloric acid. The product was then extracted withmethyl tert-butyl ether. The organic phase was washed with water, driedover magnesium sulfate and finally evaporated down. Purification of thecrude product was carried out by means of column chromatography oversilica gel (eluent: 1:1 cyclohexane/ethyl acetate). Yield: 9.1 g.

¹ H-NMR (250 MHz; in d⁶ -dimethyl sulfoxide): δ ppm!=7.78 (d,1H), 8.24(d,1H).

Preliminary stage 9.3

4,6-Dichlorobenzothiazole

A solution of 98 mmol of methyl magnesium chloride in tetrahydrofruanwas added dropwise to a solution of 14 g (49 mmol) of2-bromo-4,6-dichlorobenzothiazole in 200 ml of tetrahydrofuran, whichsolution had been cooled to -78° C. After 2 hours, acidification waseffected with 10% strength hydrochloric acid and the product was thenextracted with diethyl ether. The organic phase was washed with water,saturated aqueous sodium bicarbonate solution and water, dried oversodium sulfate and finally evaporated down. Purification of the crudeproduct was effected by means of silica gel chromatography (eluent: 5:1petroleum ether/methyl tert-butyl ether). Yield: 5.2 g.

¹ H-NMR (250 MHz; in d⁶ -dimethyl sulfoxide): δ ppm!=7.79 (d,1H), 8.36(d,1H), 9.53 (s,1H).

Preliminary stage 9.4

4,6-Dichloro-7-nitrobenzothiazole

5.2 g (26 mmol) of 4,6-dichlorobenzothiazole were reacted similarly topreliminary stage 4.2. Yield: 5.8 g.

¹ H-NMR (270 MHz; in d⁶ -dimethyl sulfoxide): δ ppm!=8.17 (s,1H), 9.65(s,1H).

Preliminary stage 9.5

7-Amino-4,6-dichlorobenzothiazole

5.8 g of 4,6-dichloro-7-nitrobenzothiazole were reacted similarly topreliminary stage 4.3. Yield: 3.0 g.

¹ H-NMR (250 MHz; in d⁶ -dimethyl sulfoxide): δ ppm!=6.11 (s,2H), 7.52(d,1H), 9.38 (d,1H).

EXAMPLE 10 Ethyl 3-4-chloro-6-fluoro-7-(6-trifluoromethyl-2,4(1H,3H)-dioxopyrimidin-3-yl)benzothiazol-2-yl!acrylate(compound I.28)

4.0 g (13 mmol) of ethyl3-(7-amino-4-chloro-6-fluorobenzothiazol-2-yl)acrylate were reactedsimilarly to Example 5.

Yield: 0.8 g.

¹ H-NMR (270 MHz; in CDCl₃): δ ppm!=1.34 (t,3H), 4.30 (q,2H), 6.31(s,1H), 6.75 (d,1H), 7.52 (d,1H), 7.88 (d,1H), 9.30 (s,1H).

Preliminary stage 10.1

Ethyl 3-(4-chloro-6-fluorobenzothiazol-2-yl)acrylate

150 g (1.48 mol) of ethyl acrylate, 11.4 g (85 mmol) of copper (II)chloride and 11.4 g (0.11 mol) of tert-butyl nitrite were added to asolution of 12 g (59 mmol) of 2-amino-4-chloro-6-fluorobenzothiazole in0.4 1 of acetonitrile. Stirring was carried out for 3 days, after whichthe mixture was acidified with dilute hydrochloric acid. The product wasextracted with methyl tert-butyl ether, after which the extracts weredried over magnesium sulfate and finally evaporated down. Purificationof the crude product was effected by means of column chromatography oversilica gel (eluent: 19:1 cyclohexane/methyl tert-butyl ether). Yield:9,0 g.

¹ H-NMR (400 MHz; in CDCl₃): δ ppm!=1.36 (t,3H), 4.30 (q,2H), 6.74(d,1H), 7.31 (dd,1H), 7.48 (dd,1H), 7.90 (d,1H).

Preliminary stage 10.2

Ethyl 3-(4-chloro-6-fluoro-7-nitrobenzothiazol-2-yl)acrylate

8.0 g (28 mmol) of ethyl 3-(4-chloro-6-fluorobenzothiazol-2-yl)-acrylatewere reacted similarly to preliminary stage 4.2.

Yield: 9.2 g.

¹ H-NMR (270 MHz; in d⁶ -dimethyl sulfoxide): δ ppm!=1.31 (t,3H), 4.26(q,2H), 7.08 (d,1H), 7.88 (d,1H), 8.22 (d,1H).

Preliminary stage 10.3

Ethyl 3-(7-amino-4-chloro-6-fluorobenzothiazol-2-yl)acrylate

10 g (30 mmol) of ethyl3-(4-chloro-6-fluoro-7-nitrobenzo-thiazol-2-yl)acrylate were reactedsimilarly to preliminary stage 4.3.

Yield: 7.8 g.

¹ H-NMR (250 MHz; in d⁶ -dimethyl sulfoxide): δ ppm!=1.30 (t,3H), 4.25(q,2H), 6.01 (s,2H), 6.82 (d,1H), 7.55 (d,1H), 7.82 (d,1H).

EXAMPLE 113-(4-Chloro-2-ethyl-6-fluorobenzothiazol-7-yl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione(compound I.18)

5.4 g of 7-amino-4-chloro-2-ethyl-6-fluorobenzothiazole were reactedsimilarly to Example 5. Yield: 5.7 g; mp.: 178° to 180° C.

Preliminary stage 11.1

4-Chloro-2-ethyl-6-fluorobenzothiazole

A solution of 0.2 mol of ethyl magnesium bromide in diethyl ether wasadded to a solution of 22.0 g (0.1 mol) of2,4-dichloro-6-fluorobenzothiazole and 3.3 g (5 mmol) ofdichlorobis(triphenylphosphine)nickel in 0.5 1 of diethyl ether.Stirring was carried out for 2 hours, after which the mixture was pouredonto saturated aqueous ammonium chloride solution. The product wasextracted with diethyl ether. The combined organic phases were washedwith water, dried over magnesium sulfate and finally evaporated down.Purification of the crude product was effected by means of silica gelchromatography (eluent: 8:2 cyclohexane/methyl tert-butyl ether). Yield:10.3 g.

¹ H-NMR (270 MHZ; in CDCl₃): δ ppm!=1.46 (t,3H), 3.16 (q,2H), 7.25(dd,1H), 7.43 (dd,1H).

Preliminary stage 11.2

4-Chloro-2-ethyl-6-fluoro-7-nitrobenzothiazole

9 g (42 mmol) of 4-chloro-2-ethyl-6-fluorobenzothiazole were reactedsimilarly to preliminary stage 4.2. Yield: 8.4 g; mp.: 70° to 73° C.

Preliminary stage 11.3

7-Amino-4-chloro-2-ethyl-6-fluorobenzothiazole

8.5 g (33 mmol) of 4-chloro-2-ethyl-6-fluoro-7-nitrobenzothiazole werereacted similarly to preliminary stage 4.3. Yield: 6.4 g.

¹ H-NMR (270 MHz; in CDCl₃): δ ppm!=7.2 (t,3H), 3.16 (q,2H), 7.21(d,1H), 8.00 (s,2H).

Table 5 shows, in addition to the above active ingredients, furthersubstituted benzothiazoles of the formula I, which were prepared in thesame manner or can be prepared in a similar manner:

                                      TABLE 5    __________________________________________________________________________     ##STR58##    No.  R.sup.1            R.sup.4              Y  R.sup.6   .sup.1 H-NMR δ in ppm!/MS m!/Mp.    __________________________________________________________________________    I.1  H  H -- Cl        6.25(s, 1H), 7.00(d, 1H), 7.37(d, 1H)    I.2  CH.sub.3            H -- Cl        3.48(s, 3H), 6.40(s, 1H), 7.27(d, 1H),    (=Ia.1)                7.65(d, 1H)    I.3  CH.sub.3            H O  C.sub.2 H.sub.5                           1.48(t, 3H), 3.56(s, 3H), 4.70(q, 2H),    (=Ic.19)               6.40(s.1H), 7.04(d, 1H), 7.48(d, 1H)    I.4  H  F -- Cl        6.43(s, 1H), 8.06(d, 1H)    I.5  CH.sub.3            F -- Cl        3.62(s, 3H), 6.40(s, 1H), 7.46(d, 1H)    (=Ia.2)    I.6  H  F O  C.sub.2 H.sub.5                           1.49(t, 3H), 4.65(q, 2H), 6.50(s, 1H),                           7.82(d, 1H)    I.7  CH.sub.3            F O  C.sub.2 H.sub.5                           1.47(t, 3H), 3.56(s, 3H), 4.67(q, 2H),    (=Ic.20)               6.38(s, 1H), 7.33(d, 1H)    I.8  H  F O  n-C.sub.3 H.sub.7                           0.95(t, 3H), 1.72(sex, 2H), 4.53(t, 2H),                           6.46(s, 1H)7.82(d, 1H)    I.9  CH.sub.3            F O  n-C.sub.3 H.sub.7                           1.04(t, 3H), 1.88(sex, 2H), 3.58(s, 3H),    (=Ic.23)               4.58(t, 2H), 6.39(s, 1H), 7.32(d, 1H)    I.10 H  F S  CH.sub.3  2.78(s, 3H), 6.22(s, 1H), 7.35(d, 1H)    I.11 CH.sub.3            F S  CH.sub.3  2.78(s, 3H), 3.56(s, 3H), 6.38(s, 1H),    (=Ie.17)               7.38(d, 1H)    I.12 H  H O  C.sub.2 H.sub.5                           1.50(t, 3H), 4.69(q, 2H), 6.26(s, 1H),                           7.05(d, 1H), 7.50(d, 1H)    I.13 H  F S  C.sub.2 H.sub.5                           1.50(t, 3H), 3.32(q, 2H), 6.33(s, 1H),                           7.15(d, 1H)    I.14 CH.sub.3            F S  C.sub.2 H.sub.5                           1.51(t, 3H), 3.37(q, 2H), 3.59(s, 3H),    (=Ie.20)               6.40(s, 1H), 7.40(d, 1H)    I.15 C.sub.2 H.sub.5            F -- Cl        1.39(t, 3H), 4.06(q, 2H), 6.38(s, 1H),                           7.49(d, 1H)    I.16 H  F -- CH.sub.3  2.85(s, 3H), 6.26(s, 1H), 7.45(d, 1H)    I.17 CH.sub.3            F -- CH.sub.3  2.85(s, 3H), 3.59(s, 3H), 6.41(s, 1H),    (=Ia.17)               7.45(d, 1H)    I.18 H  F -- C.sub.2 H.sub.5                           1.36(t, 3H), 3.17(q, 2H), 6.55(s, 1H),                           7.92(d, 1H)    I.19 CH.sub.3            F -- C.sub.2 H.sub.5                           1.45(t, 3H), 3.15(q, 2H), 3.60(s, 3H),    (=Ia.20)               6.41(s, 1H), 7.46(d, 1H)    I.20 H  Cl              S  CH.sub.3  2.82(s, 3H), 6.27(s, 1H), 7.66(s, 1H)    I.21 CH.sub.3            Cl              S  CH.sub.3  2.81(s, 3H), 3.60(s, 3H), 6.40(s, 1H),    (=Ie.18)               7.65(s, 1H)    I.22 CH.sub.3            F SO CH.sub.3  441 M!.sup.+, 426 M-CH.sub.3 !.sup.+    (=Ig.17)    I.23 CH.sub.3            F SO.sub.2                 CH.sub.3  3.43(s, 3H), 3.60(s, 3H), 6.42(s, 1H),    (=Ii.17)               7.64(d, 1H)    I.24 H  Cl              -- CH.sub.3  2.86(s, 3H), 6.58(s, 1H), 8.04 (s, 1H)    I.25 CH.sub.3            Cl              -- CH.sub.3  2.86(s, 3H), 3.45(s, 3H), 6.71(s, 3H),    (=Ia.18)               8.06(s, 3H)    I.26 H  Cl              -- H         6.56(s, 1H), 8.12(s, 1H), 9.57(s, 1H)    I.27 CH.sub.3            Cl              -- H    (=Ia.15)    I.28 H  F -- CHCHCO.sub.2 C.sub.2 H.sub.5                           1.34(t, 3H), 4.30(q, 2H), 6.31(s, 1H),                           6.75(d, 1H), 7.52(d, 1H), 7.88(d, 1H),                           9.30(s, 1H)    I.29 CH.sub.3            F -- CHCHCO.sub.2 C.sub.2 H.sub.5                           1.34(t, 3H), 3.60(s, 3H), 4.30(q, 2H),    (=Ia.182)              6.42(s, 1H), 6.74(d, 1H), 7.51(d, 1H),                           7.87(d, 1H)    I.30 H  F S  n-C.sub.3 H.sub.7                           1.01(t, 3H), 1.80(sext, 2H), 3.35(t, 2H),                           6.43(s, 1H), 7.90(d, 1H)    I.31 CH.sub.3            F S  n-C.sub.3 H.sub.7                           1.08(t, 3H), 1.87(sext, 2H), 3.33(t, 2H),    (=Ie.23)               3.58(s, 3H), 6.39(s, 1H), 7.38(d, 1H)    I.32 H  Cl              S  C.sub.2 H.sub.5                           1.45(t, 3H), 3.39(q, 2H), 6.52(s, 1H),                           8.02(s, 1H)    I.33 CH.sub.3            Cl              S  C.sub.2 H.sub.5                           150-153° C.    (=Ie.21)    I.34 H  Cl              S  n-C.sub.3 H.sub.7                           1.01(t, 3H), 1.80(sext, 2H), 3.36(t, 2H),                           6.54(s, 1H), 8.02(s, 1H)    I.35 CH.sub.3            Cl              S  n-C.sub.3 H.sub.7                           1.08(t, 3H), 1.87(sext, 2H), 3.32(t, 2H),    (=Ie.24)               3.58(s, 3H), 6.38(s, 1H), 7.61(s, 1H)    I.36 H  Cl              S  CH(CH.sub.3).sub.2                           1.49(d, 6H), 4.07(m, 1H), 6.52(s, 1H),                           8.03(s, 1H)    I.37 CH.sub.3            Cl              S  CH(CH.sub.3).sub.2                           1.52(d, 6H), 3.59(s, 3H), 4.14(m, 1H),    (=Ie.27)               6.39(s, 1H), 7.62(s, 1H)    I.38 H  F -- CH(CH.sub.3).sub.2    I.39 CH.sub.3            F -- CH(CH.sub.3).sub.2    (=Ia.26)    I.40 H  Cl              -- Cl    I.41 CH.sub.3            Cl              -- Cl        429 M!.sup.+, 394 M-Cl!.sup.+    __________________________________________________________________________

EXAMPLE 12 7-Amino-4-chloro-6-fluoro-2-(methylsulfinyl)benzothiazole(compound XIV.1; =XIVa.2)

23.0 g of 4-chloro-6-fluoro-2-methylsulfinyl-7-nitrobenzothiazole wereadded in small portions to a mixture of 455 ml of water, 32.6 ml ofconcentrated hydrochloric acid and 37.2 g of iron powder at the refluxtemperature. After the end of the addition, refluxing was continued fora further 2 hours. The mixture was cooled and 200 ml of ethyl acetatewere then added, after which the inorganic salts were filtered off. Theorganic phase was washed with water, dried over sodium sulfate andfinally evaporated down. The crude product obtained could be furtherprocessed without further purification.

¹ H-NMR (250 MHz; in d⁶ -dimethyl sulfoxide): see Table 6.

Table 6 shows, in addition to the abovementioned aniline derivativesXIV, also further aniline derivatives XIV which were prepared in thesame manner or can be prepared in a similar manner:

    ______________________________________     ##STR59##    No.    R.sup.4                  Y      R.sup.6                              .sup.1 H-NMR δ in ppm!    ______________________________________    XIV.1  F      SO     CH.sub.3                              3.20(s, 3H), 6.15(s, 2H), 7.60 d, 1H)    (=XIVa.2)    XIV.2  Cl     SO.sub.2                         CH.sub.3                              3.61(s, 3H), 6.50(s, 2H), 7.77(s, 1H)    (=XIVb.3)    XIV.3  F      SO     C.sub.2 H.sub.5                              1.21(t, 3H), 3.18(m, 1H), 3.40(m, 1H),    (=XIVa.6)                 6.14(s, 2H), 7.60(d, 1H)    ______________________________________

EXAMPLE 13 4,6-Dichloro-7-isocyanato-2-(methylsulfonyl)benzothiazole(compound XI.1; =XIb.3)

5 g (17 mmol) of 7-amino-4,6-dichloro-2-(methylsulfonyl)benzothiazoleand 17 g (85 mmol) of diphosgene in 200 ml of toluene were refluxed for8 hours, after which the reaction mixture was evaporated down.

The crude product obtained was reacted further without purification.

IR (film): ν=2272 cm⁻¹.

EXAMPLE 14

4-Chloro-2-ethylsulfinyl-6-fluoro-7-isocyanatobenzothiazole (compoundXI.2; =XIa.6) was prepared similarly to Example 7.

IR (film): ν=2264 cm⁻¹.

Use Examples (herbicidal activity)

The herbicidal action of the substituted benzothiazoles I weredemonstrated by the following greenhouse experiments:

The culture vessels used were plastic flowerpots containing loamy sandwith about 3.0% of humus as a substrate. The seeds of the test plantswere sown separately according to species.

In the preemergence treatment, the active ingredients suspended oremulsified in water were applied directly after sowing, by means offinely distributing nozzles. The vessels were lightly sprinkle-irrigatedin order to promote germination and growth and were then covered withtransparent plastic covers until the plants had begun to grow. Thiscovering ensures uniform germination of the test plants, provided thatthis has not been adversely affected by the active ingredients. Theapplication rate for the preemergence treatment was 0.0156 or 0.0078kg/ha a.i. (active ingredient).

For the postemergence treatment, the test plants were first grown to aheight of growth of from 3 to 15 cm, depending on the form of growth,before being treated with the active ingredients suspended or emulsifiedin water. For this purpose, the test plants were either directly sownand grown in the same vessels or grown separately as seedlings and thentransplanted into the test vessels a few days before the treatment. Theapplication rate for the postemergence treatment was 0.0156, 0.0078 or0.0039 kg/ha a.i. (active ingredient).

The plants were kept at from 10° to 25° C. or from 20° to 35° C.,according to species. The test period extended over from 2 to 4 weeks.During this time, the plants were tended and their reaction to theindividual treatments was evaluated.

Evaluation was based on a scale from 0 to 100. 100 means no emergence ofthe plants or complete destruction of at least the above-ground partsand 0 means no damage or normal course of growth.

The plants used in the greenhouse experiments consisted of the followingspecies:

    ______________________________________    Botanical Name      Common Name    ______________________________________    Amaranthus retroflexus                        redroot pigweed    Galium aparine      catchweed bedstraw    Ipomoea subspecies  morning glory    Setaria faberii     giant foxtail    Sinapis alba        white mustard    Solanum nigrum      black nightshade    Zea mays            Indian corn    ______________________________________

At an application rate of 0.0156 or 0.0078 kg/ha a.i., compound No. I.7showed a very good herbicidal action against Setaria faberii in corn inthe preemergence method. In contrast, the comparative compound A##STR60## disclosed in DE-A 42 41 658 (No. 1.01) had no effect withregard to Setaria faberii.

Compound No. I.7 was also very effective against Amaranthus retroflexus,Galium aparine, Ipomoea subspecies and Solanum nigrum in thepostemergence method at an application rate of 0.0156 or 0.0078 kg/haa.i.

At an application rate of 0.0078 or 0.0039 kg/ha a.i. in thepostemergence method, compound No. I.5 had a better herbicidal actionagainst Amaranthus retroflexus, Galium aparine, Ipomoea subspecies andSinapis alba than the comparative compound B ##STR61## disclosed in WO92/20675 (No. 1.01). Use Examples (desiccant/defoliant activity)

The test plants used were young, 4-leaf cotton plants (withoutcotyledons), which were grown under greenhouse conditions (relativehumidity from 50 to 70%; day/night temperature 27°/20° C.).

The foliage of the young cotton plants was sprayed to run off withaqueous formulations of the active ingredients (with the addition of0.15% by weight, based on the spray liquor, of the fatty alcoholalkoxylate Plurafac® LF 700¹)). The amount of water applied wasequivalent to 1000 l/ha. After 13 days, the number of dropped leaves andthe degree of defoliation in % were determined. ≠¹) -l a low-foam,nonionic surfactant from BASF AG

No defoliation occurred in the case of the untreated control plants.

We claim:
 1. A substituted benzothiazole of the formula I ##STR62## where X¹ and X², independently of one another, are each oxygen or sulfur;R¹ is hydrogen, amino, C₁ -C₆ -alkyl or C₁ -C₆ -haloalkyl, R² is hydrogen, halogen, C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₁ -C₆ -alkylthio, C₁ -C₆ -alkylsulfinyl or C₁ -C₆ -alkylsulfonyl; R³ is hydrogen, halogen or C₁ -C₆ -alkyl; R⁴ is hydrogen or halogen; R⁵ is cyano, halogen, C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₁ -C₆ -alkoxy or C₁ -C₆ -haloalkoxy; Y is a chemical bond, oxygen, sulfur, --SO-- or --SO₂ --; R⁶ is hydrogen, cyano, halogen, C₃ -C₆ -cycloalkyl, C₁ -C₆ -haloalkyl, C₃ -C₆ -alkenyl, C₃ -C₆ -haloalkenyl, C₃ -C₆ -alkynyl or C₁ -C₆ -alkyl, it being possible for the stated cycloalkyl, alkyl, alkenyl and alkynyl radicals to be substituted by cyano, C₁ -C₆ -alkoxy, C₁ -C₆ -alkylthio, (C₁ -C₆ -alkoxy)carbonyl, C₁ -C₆ -alkylaminocarbonyl, di(C₁ -C₆ -alkyl)aminocarbonyl, (C₁ -C₆ -alkyl)carbonyloxy, halo-C₁ -C₆ -alkoxy, halo-C₁ -C₆ -alkylthio or C₃ -C₆ -cycloalkyl,with the proviso that R⁶ may be cyano only when Y is a chemical bond, oxygen or sulfur and R⁶ may be halogen only when Y is a chemical bond,and the agriculturally useful salts of I.
 2. A herbicide containing a herbicidal amount of at least one substituted benzothiazole of the formula I or of an agriculturally useful salt of I, as claimed in claim 1, and at least one inert liquid or solid carrier and, optionally, at least one surfactant.
 3. A plant desiccant or defoliant containing an amount, effective for desiccation or defoliation, of at least one substituted benzothiazole of the formula I or of an agriculturally useful salt of I, as claimed in claim 1, and at least one inert liquid or solid carrier and, optionally, at least one surfactant.
 4. A process for the preparation of a herbicide, wherein a herbicidal amount of at least one substituted benzothiazole of the formula I or of an agriculturally useful salt of I, as claimed in claim 1, and at least one inert liquid or solid carrier and, optionally, at least one surfactant are mixed.
 5. A process for the preparation of a desiccant or defoliant, wherein an amount, effective for desiccation or defoliation, of at least one substituted benzothiazole of the formula I or of an agriculturally useful salt of I, as claimed in claim 1, and at least one inert liquid or solid carrier and, optionally, at least one surfactant are mixed.
 6. A method for controlling undesirable plant growth, wherein a herbicidal amount of at least one substituted benzothiazole of the formula I or of an agriculturally useful salt of I, as claimed in claim 1, is allowed to act on plants, on their habitat or on seed.
 7. A method for desiccating or defoliating plants, wherein an amount, effective for desiccation or defoliation, of at least one substituted benzothiazole of the formula I or of an agriculturally useful salt of I, as claimed in claim 1, is allowed to act on plants.
 8. A process for the preparation of a substituted benzothiazole of the formula I as claimed in claim 1, wherein eithera) a substituted benzothiazole of the formula I where R¹ is hydrogen and X¹ is oxygen ##STR63## is alkylated or aminated, or b) a substituted benzothiazole of the formula I where X² is oxygen ##STR64## is treated with a sulfurizing reagent, or c) a substituted benzothiazole of the formula I, in which YR⁶ is chlorine, bromine, --SO₂ -alkyl or --SO₂ -haloalkyl, is reacted with an alcohol HOR⁶ or mercaptan HSR⁶,or d) a substituted benzothiazole of the formula I where X¹ and X² are each oxygen and Y is sulfur or --SO-- ##STR65## is oxidized, or d) an enaminoester of the formula IV ##STR66## or an enaminocarboxylate of the formula V ##STR67## is cyclized, or f) a 2-aminobenzothiazole of the formula VI ##STR68## is diazotized and the product is subjected to a Sandmeyer reaction or a variant thereof. 